N-Heterocyclic Carbene Complexes Of Metal Imido Alkylidenes And Metal OXO Alkylidenes, And The Use Of Same

ABSTRACT

The invention relates to an N-heterocyclic carbene complex of general formulas I to IV (I) (II) (III) (IV), according to which A1 stands for NR2 or PR2, A2 stands for CR2 R2′, NR2, PR2, 0 or S, A3 stands for N or P, and C stands for a carbene carbon atom, ring B is an unsubstituted or a mono or poly-substituted 5 to 7-membered ring, substituents R2 and R2′ stand, inter alia, for a linear or branched C1-Cw-alkyl group and, if N and N each stand for NR2 or PR2, are the same or different, M in formulas I, II, III or IV stands for Cr, Mo or W, X 1 or X2 in formulas I to IV are the same or different and represent, inter alia, C1-C1s carboxylates and C1-C1s-alkoxides, Y is inter alia oxygen or sulphur, Z is inter alia a linear or branched C1-Cw-alkylenoxy group, and R 1 and R1′ in formulas I to IV are, inter alia, an aliphatic or aromatic group. These compounds are particularly suitable for use as catalysts for olefin metathesis reactions and have the advantage, compared to known Schrock carbene complexes, of displaying clearly increased tolerance to functional groups such as, in particular, aldehydes, secondary amines, nitriles, carboxylic acids and alcohols.

The invention relates to N-heterocyclic carbene complexes of metal imidoalkylidenes and metal oxo alkylidenes, and to the use thereof ascatalysts in olefin metathesis reactions.

Alkylidene complexes of metals of group VI (Cr, Mo, W) in their highestoxidation state (“high oxidation state metal alkylidenes”) have beenknown for many years (Chem. Rev. 2002, 102, 145; Chem. Commun. 2005,2773; Chem. Rev. 2009, 109, 3211). Compounds of the general formulaeM(NR) (CHR′)X¹X² and M(O) (CHR′)X¹X² in which R is alkoxy, an aryl oradamantyl radical, R′ is t-butyl or CMe₂Ph and X¹ and X² are alkoxy,aryloxy, pyrrolide radicals and the like, while M is a metal in the formof molybdenum or tungsten, are also referred to as “Schrock carbenes” or“Schrock catalysts”. Compounds of this kind have high activity invarious (asymmetric and desymmetrizing) olefin metathesis reactions, andhave been used successfully in ring-closing metatheses,cross-metatheses, ring-opening cross-metatheses, (cross-)ene-ynemetatheses, ring-closing ene-yne metatheses, cross-ene-diyne metatheses,tandem ring-opening-ring-closing metatheses, ring-opening metathesispolymerizations (ROMP), 1-alkyne polymerizations, acyclic metathesispolymerizations (ADMET) or in cyclopolymerizations of α,ω-diynes. In thecase of the known Schrock catalysts, however, the low tolerance thereofwith respect to functional groups, such as, more particularly, ketones,aldehydes and isocyanates, and protic compounds such as alcohols,thiols, carboxylic acids, and primary or secondary amines, has beenfound to be disadvantageous. In the case of substrates that contain suchfunctional groups, relatively rapid deactivation or breakdown of thecatalyst has therefore been observed.

For this reason, there is a need for catalysts of the “Schrock type”having maximum tolerance with respect to various functional groups andsimultaneously having maximum activity. It is accordingly an object ofthe invention to propose an advantageous catalyst system that remediesthese shortcomings.

This object is achieved in accordance with the invention by anN-heterocyclic carbene complex of the general formula I, II, III or IV

which is characterized in that A¹ is NR² or PR², A² is CR²R^(2′), NR²,PR², O or S, A³ is N or P, C is a carbene carbon atom,the ring B is an unsubstituted or a mono- or polysubstituted 5- to7-membered ring which, as well as A¹, A² and/or A³, may contain furtherheteroatoms in the form of nitrogen, phosphorus, oxygen or sulfur andwherein the substituents may have the definition described for R²,the substituents R² and R^(2′) are independently H, a linear, partlycyclic or branched C₁-C₁₈-alkyl, especially a C₁-C₇-alkyl, a linear,partly cyclic or branched C₂-C₁₈-alkenyl, especially a C₂-C₇-alkenyl, aC₃-C₁₂-cycloalkyl, especially a C₃-C₆-cycloalkyl, a linear, partlycyclic or branched C₆-C₁₀₀-polyoxaalkyl, especially C₆-C₃₀-polyoxaalkyl,a C₅-C₁₄-aryl or -heteroaryl radical, a C₅-C₁₄-aryloxy, a linear, partlycyclic or branched C₁-C₁₈-perfluoroalkyl, especiallyC₁-C₇-perfluoroalkyl, a linear, partly cyclic or branchedC₁-C₁₈-perchloroalkyl, especially a C₁-C₇-perchloroalkyl, a linear,partly cyclic or branched part-fluorinated C₁-C₁₈-alkyl, especially apart-fluorinated C₁-C₇-alkyl, a linear, partly cyclic or branchedpart-chlorinated C₁-C₁₈-alkyl, especially a part-chlorinatedC₁-C₇-alkyl, a per- or part-fluorinated C₆-C₁₄-aryl, a per- orpart-chlorinated C₅-C₁₄-aryl radical, and, when A¹ and A² are each NR²or PR², R² may be the same or different, or R² and R^(2′) together are alinear or branched C₁-C₁₈-alkylene, especially a C₁-C₇-alkylene radical,M in the formulae I, II, III and IV is Cr, Mo or W,X¹ and X² in formulae I to IV are the same or different and are selectedfrom the group comprising C₁-C₁₈ carboxylates, C₁-C₁₈-alkoxides,fluorinated C₁-C₁₈alkoxides, C₁-C₁₈ mono- or polyhalogenatedcarboxylates, unsubstituted or mono- or polysubstituted C₆-C₁₈ mono-,bi- or terphenoxides, trifluoromethanesulfonate, non-coordinatinganions, especially tetrakis(3,5-bis-(trifluoromethyl)phenyl)borate,tetrakis(penta-fluorophenyl)borate,tetrakis(nonafluoro-t-butoxy)-aluminate, tetrafluoroborate,hexafluorophosphate and hexafluoroantimonate, where the substituents onthe mono-, bi- or terphenoxides, in addition to halogen, may have thesame definition as R²,Y is oxygen, sulfur, an N-adamantyl, an N-tert-butyl, a C₆-C₁₄—N-arylradical, especially a C₆-C₁₀—N-aryl radical, where the aryl radical maybe mono- or polysubstituted by halogen, a linear or branched C₁-C₁₈alkyl, a linear or branched C₁-C₁₈ alkyloxy or an unsubstituted orsubstituted phenyl radical wherein the substituents have the samedefinition as R²,Z is a linear, partly cyclic or branched C₁-C₁₀-alkyleneoxy, especiallya C₁-C₅-alkyleneoxy, a linear, partly cyclic or branchedC₁-C₁₀-alkylenethio, especially a C₁-C₅-alkylenethio, a linear, partlycyclic or branched C₁-C₁₀-alkylene-NR², especially a C₁-C₅-alkylene-NR²,a C₆-C₁₀-aryleneoxy, a per- or part-fluorinated C₆-C₁₄-aryleneoxy, aper- or part-chlorinated C₆-C₁₄-aryleneoxy, a per- or part-brominatedC₆-C₁₄-aryleneoxy, a C₆-C₁₄-arylenethio, a per- or part-fluorinatedC₆-C₁₄-arylenethio, a per- or part-chlorinated C₆-C₁₄-arylenethioradical, a per- or part-brominated C₆-C₁₄-arylenethio or aC₆-C₁₄-arylene-NR², a per- or part-fluorinated C₆-C₁₄-arylene-NR², aper- or part-chlorinated C₆-C₁₄-arylene-NR², a per- or part-brominatedC₆-C₁₄-arylene-NR², a C₆-C₁₄-arylene-PR², a per- or part-fluorinatedC₆-C₁₄-arylene-PR², a per- or part-chlorinated C₆-C₁₄-arylene-PR², aper- or part-brominated C₆-C₁₄-arylene-PR², a carboxyl, a thiocarboxylor a dithiocarboxyl group, andR¹ and R^(1′) in the formulae I to IV are independently H or analiphatic or aromatic radical, especially a linear or branched C₁-C₁₈alkyl group, preferably in the form of a tert-butyl or CMe₂Ph group, oran unsubstituted or mono- or polysubstituted C₆-C₁₄-aryl group, wherethe substituents have the definitions given for R², preferably in theform of 2-(2-propoxy)phen-1-yl, 2-methoxyphen-1-yl,2,4,5-trimethoxyphenyl or ferrocenyl.

The invention further relates to the use of these compounds as catalystin olefin metathesis reactions.

Preferred configurations of the carbene complexes of the invention areapparent from claims 2 to 6, while claims 7 to 13 describe preferredconfigurations of the use teaching of the invention.

For the inventive carbene complexes of the general formulae I to IV, itis preferable when the linear, partly cyclic or branched C₁-C₁₈-alkylgroup mentioned for the substituents R² and R^(2′) takes the form of aC₁-C₁₀-alkyl group, preferably of a C₁-C₇-alkyl group and especially ofa C₁-C₄-alkyl group. Methyl, ethyl and propyl groups are particularlysuitable.

The linear, partly cyclic or branched C₂-C₁₈-alkenyl group isappropriately in the form of a C₂-C₁₀-alkenyl group, especially in theform of a C₂-C₇-alkenyl group and preferably in the form of butenyl orhexenyl. For the C₃-C₁₂-cycloalkyl group, it is preferable when this isin the form of a C₃-C₆-cycloalkyl group. Suitable groups that should bementioned in this context are cyclopentyl and cyclohexyl. If thesubstituent R² or R^(2′) is a linear, partly cyclic or branchedC₆-C₁₀₀-polyoxaalkyl radical, it is advantageous when this is in theform of a C₆-C₃₀-polyoxaalkyl radical and especially in the form of aC₆-C₁₅-polyoxaalkyl radical. Suitable radicals are, for example,methyloxyethyl or methyloxyethyloxy.

The substituted or unsubstituted C₅-C₁₄-aryl or -heteroaryl radical ispreferably in the form of a C₆-C₁₄-aryl or -heteroaryl radical,especially a C₆-C₁₀-aryl or -heteroaryl radical. In this context,phenyl, naphthyl or ferrocenyl radicals have been found to beparticularly suitable.

Preferred substituted or unsubstituted C₅-C₁₄-aryloxy radicals areC₆-C₁₄-aryloxy radicals and especially C₆-C₁₀-aryloxy radicals.Particularly suitable unsubstituted aryloxy radicals are phenyloxy ornaphthyloxy.

The linear, partly cyclic or branched C₁-C₁₈ perfluorinated alkylradical is especially in the form of a C₁-C₁₀ perfluorinated alkylradical, preferably in the form of a C₁-C₇ perfluorinated alkyl radical,and more preferably in the form of a C₁-C₄-perfluoroalkyl radical,trifluoromethyl being the most preferred radical.

The linear, partly cyclic or branched C₁-C₁₈ perchlorinated alkylradical is likewise especially in the form of a C₁-C₁₀ perchlorinatedalkyl radical, preferably in the form of a C₁-C₇ perchlorinated alkylradical, and more preferably in the form of a C₁-C₄-perchloroalkylradical, trichloromethyl being the most preferred radical.

The linear, partly cyclic or branched part-fluorinated C₁-C₁₈-alkylradical is preferably in the form of a part-fluorinated C₁-C₁₀-alkylradical, and especially in the form of a part-fluorinated C₁-C₇-alkylradical. One example of such a radical is trifluoroethyl.

The linear, partly cyclic or branched part-chlorinated C₁-C₁₈-alkylradical is preferably in the form of a part-chlorinated C₁-C₁₀-alkylradical, and especially in the form of a part-chlorinated C₁-C₇-alkylradical. One example of such a radical is trichloroethyl.

The perfluorinated C₅-C₁₄-aryl radical is especially in the form of aperfluorinated C₆-C₁₄-aryl radical, preferably in the form of aperfluorinated C₆-C₁₀-aryl radical and more preferably in the form of apentafluorophenyl radical.

The part-fluorinated C₅-C₁₄-aryl radical is likewise especially in theform of a part-fluorinated C₆-C₁₄-aryl radical, preferably in the formof a part-fluorinated C₆-C₁₀-aryl radical and particularly andpreferably in the form of fluorophenyl.

The perchlorinated C₅-C₁₄-aryl radical is especially in the form of aperchlorinated C₆-C₁₄-aryl radical, preferably in the form of aperchlorinated C₆-C₁₀-aryl radical and particularly and preferably inthe form of a pentachlorophenyl radical.

The part-chlorinated C₅-C₁₄-aryl radical is likewise especially in theform of a part-chlorinated C₆-C₁₄-aryl radical, preferably in the formof a part-chlorinated C₆-C₁₀-aryl radical and particularly andpreferably in the form of chlorophenyl.

When A¹ and A² are each NR² or PR², the R² and R^(2′) radicals may bethe same or different.

In general, it is preferably the case for the R² substituent, if it isbonded directly to one of the A¹ or A² substituents, that it is asubstituent other than hydrogen.

If R² and R^(2′) together form a linear or branched C₁-C₁₈-alkylenegroup, it is preferably in the form of a C₁-C₇-alkylene group and morepreferably in the form of a butylene or pentylene group.

In the context of the present invention, A¹ is preferably NR².Independently thereof, A² is preferably NR² or S and more preferablyNR².

The ring B is a heterocyclic 5- to 7-membered ring having, directlyadjacent to the carbenoid carbon (i.e. the carbon atom present in theform of a carbene), at least one nitrogen atom and additionally either afurther nitrogen atom, sulfur atom, oxygen atom, phosphorus atom orquaternary carbon atom. Preferably, the heterocyclic 5- to 7-memberedring has, directly adjacent to the carbenoid carbon, at least onenitrogen atom and additionally either a further nitrogen atom or sulfuratom. The nitrogen atoms and phosphorus atoms in this case have asubstituent R² which is not in the form of hydrogen, such that thenitrogen atoms in the ring B are tertiary amines or phosphines. Inaddition, the heterocyclic ring B may be substituted, for example byphenyl, or may form a bicyclic or polycyclic system with a further,preferably aromatic ring. For example, the ring B may be a benzofused,naphthofused, phenanthrene- or anthraquinone-fused 5- to 7-memberedring. In addition, the ring B may have further substituents in the formof halogens, C₁-C₁₈ carboxylic esters, carboxamides, sulfonamides,sulfonic esters, alkyl nitriles, ethers, thioethers, amines. For thesubstituents, it is preferable when they contain 1 to 8 carbon atoms.Particularly preferred substituents are fluorine, chlorine and bromine,and also methoxycarbonyl and ethoxycarbonyl.

In the context of the present invention, it has been found to beparticularly appropriate when the ring B is a heterocycle selected fromthe group comprising 1,3-disubstituted imidazol-2-ylidenes,1,3-disubstituted imidazolin-2-ylidenes, 1,3-disubstitutedtetrahydropyrimidin-2-ylidenes, 1,3-disubstituted diazepin-2-ylidenes,1,3-disubstituted dihydrodiazepin-2-ylidenes, 1,3-disubstitutedtetrahydrodiazepin-2-ylidenes, N-substituted thiazol-2-ylidenes,N-substituted thiazolin-2-ylidenes, N-substituted triazol-2-ylidenes,N-substituted dihydrotriazol-2-ylidenes, mono- or polysubstitutedtriazolin-2-ylidenes, N-substituted thiadiazol-2-ylidenes, mono- orpolysubstituted thiadiazolin-2-ylidenes and mono- or polysubstitutedtetrahydrotriazol-2-ylidenes.

More preferably, the ring B is derived from a 1,3-disubstitutedimidazol-2-ylidene or a 1,3-disubstituted imidazolin-2-ylidene. Thesubstituent R² in this case appropriately consists of a branchedC₃-C₆-alkyl radical, especially in the form of a t-butyl, or asubstituted aryl radical, especially in the form of a2,4,6-trimethylphenyl radical (also referred to as mesityl group).

The metal in the carbene complex of the general formulae I to IV ispreferably Mo or W, especially Mo.

If at least one of the two substituents X¹ and X² is in the form of aC₁-C₁₈-carboxylate, it is preferable when this is a C₁-C₅-carboxylate.Particularly suitable carboxylates include the acetate, propionate andbenzoate.

If at least one of the two substituents X¹ and X² is in the form of aC₁-C₁₈-alkoxide, it is preferable when this is a C₁-C₈-alkoxide.Particularly suitable alkoxides include the 2-propoxide and thetert-butoxide.

If at least one of the two substituents X¹ and X² is in the form of afluorinated C₁-C₁₈-alkoxide, it is preferable when this is a fluorinatedC₁-C₈-alkoxide. Particularly suitable fluorinated alkoxides include thehexafluoro-2-propoxide and a hexafluoro-tert-butoxide.

If at least one of the two substituents X¹ and X² is in the form of amono- or polyhalogenated C₁-C₁₈-carboxylate, it is preferable when thisis a mono- or polyhalogenated C₁-C₈-carboxylate. Particularly suitablemono- or polyhalogenated C₁-C₈-carboxylates include trichloroacetate,trifluoroacetate, pentafluoro-propionate, heptafluorobutyrate andpentafluoro-benzoate.

Preferred unsubstituted or mono- or polysubstituted mono-, bi- orterphenoxides are 2,6-diphenylphenoxide,2′,2″,6′,6″-tetrakis(2-propyl)-2,6-diphenylphenoxide and2′,2′,6′,6″-tetramethyl-2,6-diphenylphenoxide.

In general, the substituents X¹ and X² should be weakly coordinating ornon-coordinating anions and especially anionic P-, B-, Al- or Sb-basedanions.

For the substituents X¹ and X², weakly coordinating substituents inparticular, for example trifluoromethanesulfonate,tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate, hexafluorophosphate andhexafluoroantimonate substituents have been found to be particularlyappropriate. In addition, it is possible to use substituents such asfluorinated and non-fluorinated C₁-C₁₈-alkoxides, especially in the formof C₁-C₄-alkoxides. Particularly suitable alkoxides are ethoxide,2-propoxide, tert-butoxide, hexafluoro-2-propoxide orhexafluoro-tert-butoxide.

Useful substituents Y include the substituents referred to above. Thefollowing applies in respect of preferred embodiments of thesesubstituents: the C₆-C₁₄—N-aryl radical is preferably in the form of aC₆-C₁₀—N-aryl radical, where the aryl radical may be mono- orpolysubstituted by halogen, C₁-C₁₈-alkyl radicals, especiallyC₁-C₈-alkyl radicals, C₁-C₁₈-alkyloxy radicals, especiallyC₁-C₈-alkyloxy radicals, particular preference being given to methoxy or2-propoxy groups, or an unsubstituted or substituted phenyl radicalwherein the substituents may have the same definition as for R².

Particularly preferred substituents Y especially include2,6-disubstituted N-aryl radicals, preferably in the form of N-phenylradicals, in which the substituents are preferably in the form of alkylradicals, such as tert-butyl, iso-propyl or methyl, or in the form ofhalogens, such as chlorine, fluorine or bromine or mixtures thereof.Further-preferred substituents Y are N-alkyl radicals in which thecarbon atom directly adjacent to the nitrogen is a quaternary carbonatom. Examples of such N-alkyl radicals are the N-tert-butyl or theN-adamantyl radical. Particularly preferred substituents Y in thecontext of the present invention are the N-2,6-dimethylphenyl radical,the 2,6-bis(2-propyl)phenyl radical, the pentafluorophenyl radical, theN-2,6-dichlorophenyl radical, the 2-tert-butylphenyl radical, theN-tert-butyl radical and the N-adamantyl radical.

The following applies in respect of preferred configurations of thesubstituent Z:

-   -   the linear, partly cyclic or branched C₁-C₁₀-alkyleneoxy group        is preferably a C₁-C₃-alkyleneoxy group, and especially an        ethyleneoxy group;    -   the linear, partly cyclic or branched C₁-C₁₀-alkylenethio group        is preferably a C₁-C₃-alkylenethio group, and especially an        ethylenethio group;    -   the linear, partly cyclic or branched C₁-C₁₀-alkylene-NR² group        is preferably a C₁-C₃-alkylene-NR² group, and especially an        ethylene-NR² group;    -   the C₆-C₁₄-aryleneoxy group is preferably a C₆-C₁₀-aryleneoxy        group, and especially a 2-phenyleneoxy group;    -   the perfluorinated C₆-C₁₄-aryleneoxy group is preferably a        perfluorinated C₆-C₁₀-aryleneoxy group, and especially a        tetrafluorophenyl-2-eneoxy group;    -   the part-fluorinated C₆-C₁₄-aryleneoxy group is preferably a        part-fluorinated C₆-C₁₀-aryleneoxy group, and especially a        fluorophenyl-2-eneoxy group;    -   the perchlorinated C₆-C₁₄-aryleneoxy group is preferably a        perchlorinated C₆-C₁₀-aryleneoxy group, and especially a        tetrachlorophenyl-2-eneoxy group;    -   the part-chlorinated C₆-C₁₄-aryleneoxy group is preferably a        part-chlorinated C₆-C₁₀-aryleneoxy group, and especially a        chlorophenyl-2-eneoxy group;    -   the perbrominated C₆-C₁₄-aryleneoxy group is preferably a        perbrominated C₆-C₁₀-aryleneoxy group, and especially a        tetrabromophenyl-2-eneoxy group;    -   the part-brominated C₆-C₁₄-aryleneoxy group is preferably a        part-brominated C₆-C₁₀-aryleneoxy group, and especially a        bromophenyl-2-eneoxy group;    -   the C₆-C₁₄-arylenethio group is preferably a C₆-C₁₀-arylenethio        group, and especially a 2-phenylenethio group;    -   the perfluorinated C₆-C₁₄-arylenethio group is preferably a        perfluorinated C₆-C₁₀-arylenethio group, and especially a        tetrafluorophenyl-2-enethio group;    -   the part-fluorinated C₆-C₁₄-arylenethio group is preferably a        part-fluorinated C₆-C₁₀-arylenethio group, and especially a        fluorophenyl-2-enethio group;    -   the perbrominated C₆-C₁₄-arylenethio group is preferably a        perbrominated C₆-C₁₀-arylenethio group, and especially a        tetrabromophenyl-2-enethio group;    -   the part-brominated C₆-C₁₄-arylenethio group is preferably a        part-brominated C₆-C₁₀-arylenethio group, and especially a        bromophenyl-2-enethio group;    -   the perchlorinated C₆-C₁₄-arylenethio group is preferably a        perchlorinated C₆-C₁₀-arylenethio group, and especially a        tetrachlorophenyl-2-enethio group;    -   the part-chlorinated C₆-C₁₄-arylenethio group is preferably a        part-chlorinated C₆-C₁₀-arylenethio group, and especially a        chlorophenyl-2-enethio group;    -   the C₆-C₁₄-arylene-NR² group is preferably a C₆-C₁₀-arylene-NR²        group, and especially an N-methylphenyl-2-ene or        N-ethylphenyl-2-ene group;    -   the perfluorinated C₆-C₁₄-arylene-NR² group is preferably a        perfluorinated C₆-C₁₀-arylene-NR² group, and especially an        N-methyltetrafluorophenyl-2-ene or        N-ethyltetrafluorophenyl-2-ene group;    -   the part-fluorinated C₆-C₁₄-arylene-NR² group is preferably a        part-fluorinated C₆-C₁₀-arylene-NR² group, and especially an        N-methylfluorophenyl-2-ene or N-ethylfluorophenyl-2-ene group;    -   the perchlorinated C₆-C₁₄-arylene-NR² group is preferably a        perchlorinated C₆-C₁₀-arylene-NR² group, and especially an        N-methyltetrachlorophenyl-2-ene or        N-ethyltetrachlorophenyl-2-ene group;    -   the part-chlorinated C₆-C₁₄-arylene-NR² group is preferably a        part-chlorinated C₆-C₁₀-arylene-NR² group, and especially an        N-methylchlorophenyl-2-ene or N-ethylchlorophenyl-2-ene group;    -   the perbrominated C₆-C₁₄-arylene-NR² group is preferably a        perbrominated C₆-C₁₀-arylene-NR² group, and especially an        N-methyltetrabromophenyl-2-ene or N-ethyltetrabromophenyl-2-ene        group;    -   the part-brominated C₆-C₁₄-arylene-NR² group is preferably a        part-brominated C₆-C₁₀-arylene-NR² group, and especially an        N-methylbromophenyl-2-ene or N-ethylbromophenyl-2-ene group;    -   the C₆-C₁₄-arylene-PR² group is preferably a C₆-C₁₀-arylene-PR²        group, and especially a P-methylphenyl-2-ene,        P-phenylphenyl-2-ene or P-ethylphenyl-2-ene group;    -   the perfluorinated C₆-C₁₄-arylene-PR² group is preferably a        perfluorinated C₆-C₁₀-arylene-PR² group, and especially a        P-methyltetrafluorophenyl-2-ene, perfluoro-P-phenylphenyl-2-ene        or P-ethyltetrafluorophenyl-2-ene group;    -   the part-fluorinated C₆-C₁₄-arylene-PR² group is preferably a        part-fluorinated C₆-C₁₀-arylene-PR² group, and especially a        P-methylfluorophenyl-2-ene or P-ethylfluorophenyl-2-ene group;    -   the perchlorinated C₆-C₁₄-arylene-PR² group is preferably a        perchlorinated C₆-C₁₀-arylene-PR² group, and especially a        P-methyltetrachlorophenyl-2-ene or        P-ethyltetrachlorophenyl-2-ene group;    -   the part-chlorinated C₆-C₁₄-arylene-PR² group is preferably a        part-chlorinated C₆-C₁₀-arylene-PR² group, and especially a        P-methylchlorophenyl-2-ene or P-ethylchlorophenyl-2-ene group;    -   the perbrominated C₆-C₁₄-arylene-PR² group is preferably a        perbrominated C₆-C₁₀-arylene-PR² group, and especially a        P-methyltetrabromophenyl-2-ene or P-ethyltetrabromophenyl-2-ene        group;    -   the part-brominated C₆-C₁₄-arylene-PR² group is preferably a        part-brominated C₆-C₁₀-arylene-PR² group, and especially a        P-methylbromophenyl-2-ene or P-ethylbromophenyl-2-ene group.

The task of the substituents R¹, R^(1′) in the context of the carbenecomplexes described here is to provide a metal alkylidene which on theone hand is stable but on the other hand still has adequate metathesisactivity. Particularly suitable substituents R¹, R^(1′) are therefore,as well as R^(1′)=H, large alkyl or aryl radicals that assure goodsteric shielding of the metal alkylidene. Accordingly, it is preferablewhen R¹ is not a hydrogen atom. Particularly appropriately, the carbonatom in R¹ directly adjacent to the metal alkylidene is a quaternarycarbon atom having no hydrogen substituents. Possible substituents forthis quaternary carbon atom include the radicals detailed for thesubstituents R². On the basis of these provisions, a suitablesubstituent R¹ can be selected by the person skilled in the art. It hasespecially been found to be advantageous when R¹ in the formulae I to IVis t-butyl, an unsubstituted or substituted phenyl, such as2-(2-propoxy)phen-1-yl, 2-methoxyphen-1-yl, 2,4,5-trimethoxyphenyl, orferrocenyl or CMe₂Ph, where the substituents on the phenyl may have thesame definition as R², but may especially be 2-(2-propoxy) or 2-methoxy.In addition, it has been found to be advantageous when the C₁-C₁₈-alkylgroup used is a C₁-C₁₀-alkyl group, and the C₆-C₁₄-aryl group used is aC₆-C₁₀-aryl group.

In a preferred embodiment, the N-heterocyclic carbene complex is anN-heterocyclic carbene complex of the general formula V or VI

which is characterized in that A¹ is NR² and A² is NR² or S, C is acarbenoid carbon atom,the ring B is a 5- to 7-membered ring which, as well as A and A², maycontain further heteroatoms in the form of nitrogen or sulfur,the substituent R² is a linear or branched C₁-C₁₀-alkyl, a linear orbranched C₂-C₁₀-alkenyl, especially a C₃-C₆-cycloalkyl, a linear orbranched C₆-C₁₀-polyoxaalkyl, a C₅-C₁₀-aryl or a C₅-C₁₀-heteroarylradical, a C₅-C₁₀-aryloxy, a linear or branched C₁-C₁₀-perfluoroalkyl, alinear or branched C₁-C₁₀-perchloroalkyl, a linear or branched,part-fluorinated C₁-C₁₀-alkyl, a linear or branched, part-chlorinatedC₁-C₁₀-alkyl, a perfluorinated C₅-C₁₀-aryl, a part-fluorinatedC₅-C₁₀-aryl, a perchlorinated C₅-C₁₀-aryl or part-chlorinatedC₅-C₁₀-aryl radical, and, when A¹ and A² are each NR², they are the sameor different,M in the formulae V and VI is Cr, Mo or W,X¹ and X² in formulae V and VI are the same or different and areselected from the group comprising C₁-C₁₈ carboxylates,C₁-C₁₈-alkoxides, C₁-C₁₈ mono- or polyhalogenated carboxylates, mono- orpolysubstituted C₆-C₈ mono-, bi- or terphenoxides,trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate andhexafluoroantimonate, where the substituents on the mono-, bi- orterphenoxides, in addition to halogen, may have the same definition asR²,Y in the formulae V and VI is an oxo group, an N-adamantyl or an N-arylradical, where the aryl radical may be mono- or polysubstituted byhalogen, a C₁-C₁₀-alkyl, C₁-C₁₀-alkyloxy or phenyl radical, andR¹ in the formulae I and II is an aliphatic or aromatic radicalpreferably having 4 to about 20 carbon atoms.

For preferred embodiments of the substituents R¹, R², A¹, A², X¹, X² andY in the formulae V and VI, the above remarks apply analogously.

The carbene complexes of the invention may, in addition to thesubstituents shown in the formulae I to IV, or V or VI, have one or moreuncharged ligands coordinated to the metal center. The function of theseuncharged ligands is to increase the coordinative satisfaction of themetal center and to stabilize the metal complex. These ligands areelectron donors and are labile, meaning that they can be dissociatedfrom the metal center and replaced by substrate. Suitable ligands are,for example, 1,2-dimethoxyethane, tetrahydrofuran, acetonitrile,phosphines such as triphenylphosphine, tri-n-butylphosphine ortrimethylphosphine, and phosphites, for example trimethyl or triethyl ortriphenyl phosphite.

The above-described carbene complexes of the invention can be used insolution as catalyst, but it is also possible to immobilize thecomplexes on a solid support, for example with the aid of a spacergroup. The spacer group between the support material and the ring Bserves to fix the metal complexes on the solid support. The spacer groupadvantageously has to be such that the metal complex has a sufficientdistance from the support, so as to ensure good accessibility forsubstrates. The spacer group contains two functional groups by whichattachment firstly to the catalyst and secondly to the support ispossible. The distance between support and catalyst, by contrast, shouldnot be so great that bimetallic reactions between two immobilized metalcomplexes can take place. Moreover, the spacer group should be such thatit can be joined by means of simple chemical reactions either to thesupport or to the ring B, or to the metal center. In principle, allaliphatic or aromatic α,ω-difunctional compounds are useful here.

Suitable solid supports in this context especially include polymericsupports, such as those based on polystyrene/poly(divinylbenzene)(PS-DVB), crosslinked poly(methacrylate)s, crosslinkedpoly(acrylamide)s, but also crosslinked poly(norbornene)s. The supporthas the task of enabling the binding of the catalyst, and hence aheterogeneous reaction regime. For this purpose, the supportappropriately has a mean particle size in the range of 2-1000micrometers, preferably in the range of 20-200 micrometers, morepreferably in the range of 40-60 micrometers, and may be porous ornonporous.

The spacer group used in this case may appropriately be aC₁-C₂₀-alkyleneoxy group, C₁-C₂₀-α,ω-dioxoalkylene group, aC₁-C₂₀-α,ω-diaminoalkylene group, a C₁-C₂₀-α,ω-dicarboxylalkylene group,a C₆-C₁₈-dioxoarylene group, a C₆-C₁₈-diaminoarylene group or adicarboxy-C₆-C₁₈-arylene group.

When the spacer group binds directly to the metal center, it may replacean X substituent on the metal in the formulae I-III. Alternatively, thespacer group in the formulae III-IV may also be joined to a P- orN-containing Z group. Examples of suitable spacer groups in this contextare:

-   -   a linear, partly cyclic or branched aliphatic α,ω-difunctional        C₁-C₂₀-alkylene group, especially a linear, partly cyclic or        branched aliphatic α,ω-difunctional C₁-C₁₀-alkylene group, where        the two functional groups may be the same or different and are        in the form of OH, NR′H, COOH, SH, SO₃H, SO₂H, PO₃H, PO₂H,        Si(OR′)OO, Si(OR′)₂O. R′ in this case may have any of the        meanings given above for R², and may especially take the form of        N-methylpropargyl acid, where the respective functional groups        are formally in the deprotonated (anionic) form.    -   a difunctional halogenated or nonhalogenated C₆-C₁₄ aromatic        group, preferably a difunctional halogenated or nonhalogenated        C₆-C₁₀ aromatic group, where the two functional groups may be        the same or different and are in the form of OH, NR′H, COOH, SH,        SO₃H, SO₂H, PO₃H, PO₂H, Si(OR′)OO, Si(OR′)₂O. R′ in this case        may have any of the meanings given above for R², and may        especially take the form of p-aminophenol, p-aminosulfonic acid,        perfluoroaminosulfonic acid, where the respective functional        groups are formally in the deprotonated (anionic) form.

In an alternative embodiment, the solid support may also be an inorganicsupport, for example a support based on glass, silicon dioxide,zirconium oxide or titanium dioxide. Inorganic supports have theadvantage of not swelling in the presence of solvents and are thuspressure-stable support materials which in turn can be usedadvantageously for continuous heterogeneous reaction regimes. In thiscase, the spacer group used may appropriately be an amino-, hydroxy-,carboxy- or thionyl-alkylene-Si(O)₃, an amino-, hydroxy-, carboxy- orthionyl-alkylene-SiR(O)₂ group or an amino-, hydroxy-, carboxy- orthionyl-alkylene-SiRR′O group, in which useful substituents for the Rand R′ radicals are the same as those mentioned above for thesubstituent R².

The covalent attachment of the ring B to the support can be effectedusing an appropriate precursor, for example the protonated form of thering B (the ring is protonated on the carbene carbon atom) or thealkoxy- or CO₂-protected ring B which can be prepared with the aid ofone of the methods described in the literature (e.g. Adv. Synth. Catal.2006, 348, 2101; Adv. Synth. Catal. 2010, 352, 917; Chem. Eur. J. 2013,19, 11661; Adv. Synth. Catal. 2002, 344, 712; Macromol. Rapid. Commun.2004, 25, 231). The carbene in the ring B is then generated by, forexample, the addition of a base composed of the protonated form of thering B, or thermally by detachment of CO₂, for example, from theCO₂-protected ring B, and reacted with compounds of the general formulaM(Y) (CR¹R^(1′))X¹X².L_(x) in which R¹, R², X¹ and X² have thedefinitions given above, L=a neutral ligand and x may assume a value of0 to 2. The N-heterocyclic carbene complexes of the formulae I to IVmay, depending on the solvent and its composition, be in the unchargedform identified by the formula I or III or in the ionic form identifiedby the formula II or IV.

A further aspect of the present invention is concerned, as alreadyindicated above, with the use of the inventive carbene complexes of theformulae I to IV as catalyst in olefin metathesis reactions and thepolymerization of alkynes or cyclopolymerization of diynes. These olefinmetathesis reactions may all be (asymmetric and desymmetrizing) olefinmetathesis reactions catalyzable by means of Schrock carbene complexes,especially ring-closing metatheses, cross-metatheses, olefinolyses ofunsaturated compounds, such as, more particularly, the ethenolysis ofnaturally occurring vegetable oils and fats, ring-openingcross-metatheses, (cross-)ene-yne metatheses, ring-closing ene-ynemetatheses, cross-ene-diyne metatheses and tandemring-opening-ring-closing metatheses. It is thus possible to obtaincompounds that are of great significance, for example, for thepharmaceutical, agrochemical, polymer, fragrance or flavoring industry.In addition, they can be used for ring-opening metathesispolymerizations (ROMP), 1-alkyne polymerizations, acyclic metathesispolymerizations (ADMET) or cyclopolymerizations of α,ω-diynes. Thepolymers prepared in this way can be used, for example, as matrixpolymers for fiber-matrix composites, as compatibilizers or as basepolymer for fibers.

Useful substrates for these olefin metathesis reactions in principleinclude all substrates amenable to these types of metathesis reactions.For example, it is possible to employ cyclic olefins such asnorborn-2-enes, norbornadienes, cyclooctenes, cyclooctadienes,cyclooctatetraenes and/or cyclopentenes, but also alkynes such asacetylene or 2-butyne. This list is not intended to be limiting. Forinstance, the following cyclic olefins are also possible substrates:cyclopropenes, cyclobutenes, dicyclopentadienes and cyclohexenes. Thesecyclic olefins may be mono- or polysubstituted. In addition, it ispossible to convert olefins, for example ethylene, propylene andsubstituted butenes, pentenes, hexenes, heptenes, octenes and/orstyrenes, and dienes such as 1,3-butadiene, pentadienes, hexadienes,heptadienes and octadienes, within the scope of the olefin metathesisreactions described. Substrates for the olefinolysis, and especially forthe ethenolysis, of naturally occurring vegetable oils and fats aregenerally fatty acid esters and especially castor oil, palm oil orcoconut oil in combination with, for example, ethylene or butene.

A particular advantage of the inventive carbene complexes of theformulae I to IV is that they have been found to be particularlytolerant with respect to functional groups. Particular emphasis shouldbe given here to tolerance with respect to alcohols, carboxylic acids,thioethers, amines and aldehydes. Thus, olefin metathesis reactions offunctionalized olefins are directly possible, especially in the form of,for example, 5,6-bis((pentyloxy)methyl)bicyclo[2.2.1]hept-2-ene,7-oxabicyclo[2.2.1]hept-5-ene-2,3-diyl bis-(methylene)diacetate,4,4,5,5-tetrakis(ethoxycarbonyl)-1,7-octadiyne,2,2-di(prop-2-yn-1-yl)propane-1,3-diol, diallyldiphenylsilane,2-(N-cyclohexyl-methyl)norborn-5-ene,2-(N,N-dimethylaminomethyl)-norborn-5-ene),1,7-octadiyne-4,5-dicarboxylic acid, 1,6-heptadiyne-4-carboxylic acid,norborn-5-ene-2-carbaldehyde, 4,4-dicyano-1,6-heptadiyne.

A further advantage of the inventive carbene complexes of the formulae Ito IV is that they allow very high turnover numbers in some metathesisreactions. Furthermore, in the cyclopolymerization of diynes withcarbene complexes of the formulae I to IV, very high stereo- andregioselectivities are observed. Moreover, for example, in the case ofhomometatheses with carbene complexes of the formulae I to IV havingsmall N-heterocyclic carbenes and large phenoxides, high Z selectivitiesare achieved.

A particular advantage in the context of the present invention has beenfound to be that the inventive carbene complexes of the formula II orIV, by virtue of suitable choice of solvent and their composition, arein ionic form. This allows performance of the olefin metathesisreactions under biphasic conditions, which is advantageous in terms of alow metal content of the products prepared.

The performance of olefin metathesis reactions under biphasic conditionsis appropriately effected by dissolving the ionic carbene complexes ofthe formula II or IV in an organic solvent I or in an ionic liquid. Inaddition to use in conventional biphasic (liquid-liquid) reactions, thissolution can be applied to a support material in the form of a film,which can be very thin and preferably has a thickness of 0.05 to 200 μm,especially 0.5 to 10 μm, and can be introduced together with the supportinto a reaction vessel such as a reaction column. Subsequently, thesupport coated with the catalyst solution can be contacted with one ormore substrates which have optionally themselves been dissolved in asolvent II which is immiscible with the solvent I or the ionic liquidfor the compound of the formula II or IV. If no solvent II is employed,the substrates and the products formed within the particular reactionmust only have low miscibility with the solvent I or the ionic liquid.Thus, the maximum solubility of the solvent II or of the substrates, butalso of the products in the solvent I or in the ionic liquid, should be<10% by volume. The solvent II for the substrates or the substratesthemselves in this case have dissolution properties of maximumunfavorability for the catalyst compound, in order that it cannotdissolve in a substantial amount in the substrate solvent.

The reaction vessel is usefully, but not necessarily, a reaction columnhaving an inlet for the substrate solution and an outlet at the oppositeend of the reaction column. The above reaction regime is also referredto in the art as “supported ionic liquid phase” (SILP) methodology (seeTopics in Catalysis, 2006, 40, 91).

Organic solvents I used for the carbene complexes of the formula II orIV may especially be polar aprotic solvents, for exampledimethylformamide, dimethylacetamide or dimethyl sulfoxide.

Suitable ionic liquids in connection with the present invention areespecially compounds of the general formula [Q⁺]_(n) [Z]^(n−) where thecation [Q⁺]_(n) is a quaternary ammonium [R¹R²R³R⁴N⁺], phosphonium[R¹R²R³R⁴P⁺] or sulfonium [R¹R²R³S⁺] cation or an analogous quaternizednitrogen, phosphorus or sulfur heteroaromatic of the following formulae:

and the R¹, R², R³, R⁴ radicals and the R¹ to R⁸ radicals in theformulae (III) to (VIII) are independently linear, cyclic, branched,saturated or unsaturated alkyl radicals, mono- or polycyclic, aromaticor heteroaromatic radicals, or derivatives of these radicals substitutedby further functional groups. These R¹, R², R³ and R⁴ radicals may bejoined to one another. The anion [Z]^(n−) is preferably in the form of acarboxylate, halide, pseudohalide or amide, or in the form of boron,phosphorus or nitro compounds.

Particularly suitable ionic liquids are especially imidazolium salts,more preferably selected from the group comprising1-ethyl-3-methylimidazolium salts, 1,3-dimethylimidazolium salts,1,2,3-trimethylimidazolium salts, 1-butyl-3-methylimidazolium salts and1-butyl-2,3-dimethylimidazolium salts.

The solvent II which is immiscible with the solvent I or the ionicliquid for the compound of the formula II or IV is preferably analiphatic or aromatic hydrocarbon, especially toluene, xylene, pentane,hexane, heptane, octane, trichlorobenzene or chlorobenzene or mixturesthereof. In combination with the ionic complexes of formulae II and IV,it is thus assured that these complexes will not dissolve in the solventII, and hence leaching of the catalyst in a continuous reaction regimeis prevented.

Suitable support materials for the solution films of the carbenecomplexes of the formula II or IV in the context of SILP methodology areparticularly inorganic support materials, especially based on glass,zirconium oxide, titanium dioxide, silicon dioxide, or polymer-organicsupport materials, especially in the form of polymer-organic monolithicsupport materials, for example based onpoly(styrene)/poly(divinylbenzene), poly(methacrylate)s,poly(acrylamide)s or crosslinked poly(norbornene)s orpoly(cyclooctene)s. These support materials have the advantage ofswelling only slightly, if at all, and hence not causing highbackpressures in a continuous reaction regime. A continuous conversionof the substrates is advantageous because one or more substrates arepassed continuously into the reaction vessel and the resulting reactionproducts are removed continuously therefrom, which can lead in turn tohigher turnover numbers. In this way, it is possible to conduct olefinmetathesis reactions under continuous biphasic conditions (see Chem.Eur. J. 2012, 18, 14069).

The aforementioned specifications relating to the conversion ofsubstrates with carbene complexes of the formula II or IV which aredissolved in an organic solvent or in an ionic liquid and applied to asuitable support material in the form of a film likewise relate tocorresponding uses of these compounds and methods which are conductedaccording to these specifications.

The carbene complexes of the formulae I to IV have a desirably highreactivity in olefin metathesis reactions, 1-alkyne polymerization andthe cyclopolymerization of diynes, and have a significantly improvedtolerance with respect to functional groups over existing group VI metalalkylidene complexes. For example, representatives of the inventiveN-heterocyclic carbene complexes of one of the formulae I to IV arestable in the presence of aldehydes, secondary amines, carboxylic acids,nitriles and alcohols. Because of this distinct increase in functionaltolerance compared to known Schrock carbene complexes of group VImetals, the spectrum of use in olefin metathesis reactions is distinctlybroadened.

The invention is to be elucidated in detail hereinafter with referenceto examples. Some general observations are given at the outset:

Unless stated otherwise, all reaction steps were conducted in theabsence of oxygen and moisture under N₂ or Ar, either by means ofSchlenk methodology or in protective gas boxes (MBraun LabMaster 130) indry glass apparatus. The deuterated solvent CD₂Cl₂ was dried over P₂O₅and transferred under vacuum; benzene was dried and distilled over Na.Toluene, diethyl ether, THF and CH₂Cl₂ were purified by means of asolvent purification system (SPS, MBraun). Commercially availablereagents and the d₆-DMSO and CDCl₃ used were used without furtherpurification.

The NMR spectra were recorded at 20° C. with the aid of a Bruker 400spectrometer (400 MHz for proton, 101 MHz for carbon and 376 MHz forfluorine), residual signals calibrated to the internal solvents. Theshifts of the signals are reported in ppm. The IR spectra were recordedon a Bruker Vector 22 by means of ATR methodology. The molar masses andmolar mass distributions were recorded by means of high-temperature gelpermeation chromatography (HT-GPC) on three consecutive Waters StyragelHR4 4.6×300 mm columns in trichlorobenzene at 145° C. on a PSS HAT-GPCsystem. The flow rate was 1 mL/min. Narrow-distribution polystyrenestandards in the range of 162<M_(n)<6 035 000 g·mol⁻¹ (EasiVial red,yellow and green) from Polymer Laboratories were employed.

Examples 1 to 16, 34 to 36 and 38 to 53 described hereinafter relate tothe preparation of carbene complexes of the formulae I to IV, while thefurther examples 17 to 33, 37 and 55 to 57 are concerned with olefinmetathesis reactions with the aid of the carbene complexes of theinvention.

EXAMPLES

Structure of selected Mo catalysts. DIPP=2,6-di(2-propyl)phen-1-yl.

Example 1 Preparation of Mo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CH-tBu) (OTf)₂)(1)

Mo(N-2,6-Me₂-C₆H₃) (CH-tBu) (OTf)₂ (DME) (0.300 g, 0.445 mmol) weredissolved in 8 mL of benzene, and a solution of1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinylidene (0.136 g, 0.445 mmol)in 5 mL of benzene was added. The reaction solution was stirred forthree hours, the benzene was decanted off, and the residue was washedwith benzene. Yield: 0.32 g (81%, yellow powder). It was possible toobtain crystalline material by recrystallization from CH₂Cl₂. ¹H NMR(CD₂Cl₂): δ (syn isomer, 99.9%) 12.76 (s, 1, CHCMe₃, J_(CH)=118 Hz),7.06-6.61 (7H, ArH), 3.98 (4H, CH₂NC), 2.69-1.71 (24H, Me), 0.93 (s, 9H,CH₂CMe₃); ¹⁹F NMR (CD₂Cl₂): δ−74.65 (SO₃CF₃), −76.7 (SO₃CF₃). ¹³C NMR(CD₂Cl₂): δ 320.9 (CH-tBu), 208.7 (CN_(carbene)), 154.6 (C_(ipso)),140.4 (C_(ortho)), 137.1 (C_(aryl)), 136.8 (C_(aryl)), 135.7 (C_(aryl)),131.1 (CH_(aryl)), 130.5 (CH_(aryl)), 130.1 (CH_(aryl)), 128.2(C_(aryl)), 120.2 (q, CF₃, J=319 Hz), 119.8 (q, CF₃, J=320 Hz), 53.1(CMe₃), 50.7 (CH_(2-imidazolylene)), 30.5 (CMe₃), 21.3 (CH₃), 19.0(CH₃), 18.9 (CH₃); anal. calc. for C₃₆H₄₅F₆MoN₃O₆S₂.CH₂Cl₂: C, 45.54; H,4.96; N, 4.31. Found: C, 45.52; H, 4.75; N, 4.37.

Example 2 Preparation of Mo(N-2,6-Me₂-C₆H₃) (I-tBu) (CH-tBu) (OTf)₂) (2)

Mo(N-2,6-Me₂-C₆H₃)(CH-tBu)(OTf)₂ (DME) (0.100 g, 0.148 mmol) weredissolved in 3 mL of benzene. 1,3-Di-t-butylimidazol-2-ylidene (0.027 g,0.15 mmol), likewise dissolved in benzene, was added while stirring.After stirring for three hours, the liquid was decanted from theprecipitate and the residue was washed with benzene. Yield: 0.060 g(65%, yellow powder). It was possible to obtain crystalline material byrecrystallization from CH₂Cl₂. ¹H NMR (CD₂Cl₂): δ 14.60 (s, 1H, CHCMe₃,J_(CH)=121 Hz, syn isomer), 7.12-6.95 (3H, ArH), 2.60 (2H, CHNC),1.80-1.67 (24H, Me), 1.32 (s, 9H, CH₂CMe₃); ¹⁹F NMR (CD₂Cl₂): δ−77.68,−77.69, −77.70, −77.71 (CF₃SO₃), −78.06, −78.07, −78.08, −78.09(CF₃SO₃); ¹³C NMR (CD₂Cl₂): δ 329.6 (CH-tBu), 175.4 (CN_(carbene)),154.3 (C_(ipso)), 142.2 (C_(aryl)), 136.9 (C_(aryl)), 129.7 (CH_(aryl)),129.6 (CH_(aryl)), 128.9 (CH_(aryl)), 121.7 (C_(C═C)), 120.6 (C_(C═C)),119.8 (q, CF₃, J=318 Hz), 119.7 (q, CF₃, J=319 Hz), 61.7 (NCMe₃), 61.3(CMe₃), 32.8 (CMe₃), 30.5 (CMe₃), 30.1 (CMe₃), 21.1 (CH₃), 18.4 (CH₃).Anal. calc. for C₂₆H₃₉F₆MoN₃O₆S₂: C, 40.84; H, 5.27; N, 5.50. Found: C,40.88; H, 5.20; N, 5.56.

Example 3 Preparation of N-2,6-Me₂-C₆H₃) (IMesH₂)—(CHCMe₃) (OTf) (OEt)(3)

Sodium ethoxide (0.0120 g, 0.1842 mmol) was dissolved in 5 mL of diethylether:THF, 1:1. Then Mo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CH-tBu) (OTf)₂ (0.080g, 0.090 mmol) was added. After stirring for two hours, the solvent wasremoved, and the residue was dissolved in 5 mL of dichloromethane andfiltered through Celite. Recrystallization from dichloromethane gaveyellow crystalline material in 40% yield. ¹H NMR (CD₂Cl₂): δ 12.30 (s,1H, CHCMe₃), 6.94-6.65 (7H, ArH), 4.15 (4H, CH₂NC), 3.69 (2H, OCH₂CH₃),2.53-2.24 (24H, Me), 1.82 (3H, OCH₂CH₃), 1.14 (s, 9H, CH₂CMe₃); 19F NMR(CD₂Cl₂): δ −79.05 (CF₃SO₃).

Example 4 Preparation of Mo(N-2,6-Cl₂—C₆H₃) (CHCMe₃)-(OTf)₂(IMes) (4)

In a glovebox, Mo(N-2,6-Cl—C₆H₃) (CHCMe₃) (OTf)₂(DME) (0.432 g, 0.605mmol) was initially charged in a 25 mL Schlenk flask. The complex wasdissolved in 15 mL of toluene and cooled at −40° C. for 30 min.1,3-Dimesitylimidazol-2-ylidene (0.184 g, 0.605 mmol, 1 equiv.) wasdissolved in 3 mL of toluene and likewise cooled. While stirring, thecold NHC solution was added dropwise to the metal complex. The colorchanged gradually to dark orange. The reaction mixture was stirred atroom temperature for 2 h. After a few minutes, cloudiness set in and aprecipitate formed. Subsequently, the solvent was concentrated to about1/3 and the suspension was frozen for 30 min. The precipitated solidswere filtered off and washed with a little cold toluene. The crudeproduct is obtained as a yellow solid and can be recrystallized fromdichloromethane (0.450 g, 80%). ¹H NMR (400 MHz, CD₂Cl₂): δ=1.12 (s, 9H,tBu), 2.10 (s, 6H, o-Mes-Me), 2.11 (s, 6H, o-Mes-Me), 2.24 (s, 6H,p-Mes-Me), 6.68 (s, br, 2H, Mes-Ar), 6.98 (s, br, 2H, Mes-Ar), 7.14 (m,3H, Ar), 7.22 (s, 2H, N—CH—CH—N), 12.94 (s, 1H, Mo═CH); ¹³C NMR (100MHz, CD₂Cl₂): δ=18.9 (o-Mes-Me), 19.0 (o-Mes-Me), 21.3 (p-Mes-Me), 31.4(CMe ₃), 50.6 (CMe₃), 124.4, 126.4, 128.3, 129.5, 130.3, 130.9, 134.7,135.9, 136.3, 136.5, 141.0 (ipso-Mes), 149.9 (ipso-imido), 185.2(N—C—N), 327.4 (Mo═CH, J_(C—H)=119.5 Hz); ¹⁹F NMR (375 MHz, CD₂Cl₂)δ=−75.07, −76.56.

Example 5 (Preparation of Mo(N-2,6-Cl₂—C₆H₃) (CHCMe₃)-(OTf)₂(IMesH₂))(5)

In a glovebox, Mo(N-2,6-Cl—C₆H₃) (CHCMe₃) (OTf)₂(DME) (0.198 g, 0.277mmol) was initially charged in a 25 mL Schlenk flask. The complex wasdissolved in 15 mL of toluene and cooled at −40° C. for 30 min.1,3-Dimesitylimidazol-2-ylidene (0.085 g, 0.277 mmol, 1 equiv.) wasdissolved in 3 mL of toluene and likewise cooled. While stirring, thecold NHC solution was added dropwise to the metal complex. The colorchanged gradually to dark orange. The reaction mixture was stirred atroom temperature for 2 h. After a few minutes, cloudiness set in and aprecipitate formed. Subsequently, the solvent was concentrated to about1/3 and the suspension was frozen for 30 min. The precipitated solidswere filtered off and washed with a little cold toluene. The crudeproduct is obtained as a yellow solid and can be recrystallized fromdichloromethane (0.185 g, 72%).

Example 6 Preparation of Mo(N-2,6-Me₂-C₆H₃) (IMesH₂)—(CHCMe₂Ph) (OTf)₂(6)

Mo (N-2, 6-Me₂-C₆H₃) (CHCMe₂Ph) (OTf) 2 (DME) (0.20 g, 0.2720 mmol) wasinitially charged in 8 mL of benzene:1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidin-2-ylidene (0.0830 g,0.2720 mmol) was dissolved in 1 mL of benzene and added dropwise. In thecourse of this, a rapid color change from a yellow to dark red wasobserved with simultaneous formation of a precipitate.

After stirring for three hours, the benzene was then decanted off, andthe residue was washed with benzene and dried under reduced pressure.The product was isolated as a yellow solid (0.15 g, 81%). Alternatively,the yellow solid can be dissolved in a minimal amount of dichloromethaneand crystallized at −30° C. for 24 h, giving a crystalline yellowmaterial with 69% yield. ¹H NMR (CD₂Cl₂): δ=13.11 (s, 1H, CHCMe₂Ph,J_(CH)=114 Hz), 7.19-6.95 (m, 9H, ArH), 6.51 (s, 2H, ArH), 3.97 (s, 4H,CHNC), 2.69-1.71 (s, 27H, Me), 1.25 (s, 3H, CHCMe₂Ph) ppm; ¹⁹F NMR(CD₂Cl₂): δ=−74.59 (s, CF₃SO₃, trans to the NHC ligand), −76.53 (s,CF₃SO₃); ¹³C NMR (CD₂Cl₂): δ=317.4 (CHCMe₃), 208.7 (CN_(carbene)), 154.6(C_(ipso)), 149.0, 140.4 (C_(ortho)), 137.0 (C_(aryl)), 136.4(C_(aryl)), 135.6 (C_(aryl)), 130.9 (C_(aryl)), 130.5 (C_(aryl)), 130.2(C_(aryl)), 128.4 (C_(aryl)), 128.2 (C_(aryl)), 126.9 (C_(aryl)), 125.9(C_(aryl)), 121.6 (q, CF₃, J=319 Hz), 118.5 (q, CF3, J=320 Hz), 56.8(CMe₂Ph), 53.1 (CH₂ imidazolylidene), 32.9 (CMe₂Ph), 29.6 (CMe₂Ph), 21.3(CH₃), 19.0 (CH₃), 18.9 (CH₃); elemental analysis: C₄₁H₄₇F₆MoN₃O₆S₂;calculated: C, 51.68; H, 5.02; N, 4.41. found: C, 51.81; H, 4.88; N,4.35.

Example 7 Preparation of Mo(N-2,6-Me₂-C₆H₃) (IMes)-(CHCMe₂Ph) (OTf)₂ (7)

Mo (N-2, 6-Me₂-C₆H₃) (CHCMe₂Ph) (OTf)₂(DME) (0.1500 g, 0.204 mmol) wasdissolved in 6 mL of benzene, adding to the initially charged solutionof 1,3-bis(2,4,6-trimethylphenyl)-2-imidazol-2-ylidene (0.0620 g, 0.2040mmol) in a 1 mL of benzene. The color changed immediately from yellow todark red with simultaneous formation of a precipitate. The reactionmixture was stirred for three hours and then the solvent was decanted.The residue was washed with benzene and dried under reduced pressure. Ayellow solid was obtained (0.13 g, 85%). The yellow product can berecrystallized from a minimal amount of dichloromethane at −30° C.(65%). ¹H NMR (CD₂Cl₂): δ=13.18 (s, 1H, CHCMe₂Ph, J_(CH)=118 Hz),7.21-6.95 (m, 9H, ArH), 6.56 (s, 2H), 4.29 (s, 2H, CHNC), 2.60-1.97 (s,27H, Me), 1.29 (s, 3H, CHCMe₂Ph) ppm; ¹⁹F NMR (CD₂Cl₂): δ=−74.92 (s,CF₃SO₃, trans to the NHC ligand), −76.53 (s, CF₃SO₃); ¹³C NMR (CD₂Cl₂):δ=317.0 (CHCMe₃), 184.3 (CN_(carbene)), 154.8 (C_(ipso)), 149.0, 141.3(C_(ortho)), 136.4 (C_(aryl)), 135.9 (C_(aryl)), 135.5 (C_(aryl)), 130.6(C_(aryl)), 130.1 (C_(aryl)), 130.0 (C_(aryl)), 128.6 (C_(aryl)), 128.2(C_(aryl)), 126.9 (C_(aryl)), 126.4 (C_(aryl)), 125.9 (C_(aryl)), 121.6(C_(C═C)), 121.4 (C_(C═C)), 118.4 (q, CF₃, J=318 Hz), 118.3 (q, CF₃,J=319 Hz), 56.8 (CMe₂Ph), 33.2 (CMe₂Ph), 29.8 (CMe₂Ph), 21.4 (CH₃), 20.6(CH₃), 18.7 (CH₃); elemental analysis: C₄₁H₄₅F₆MoN₃O₆S₂; calculated: C,51.79; H, 4.88; N, 4.42. found: C, 51.73; H, 4.80; N, 4.39.

The catalyst Mo (N-2,6-Me₂-C₆H₃) (IMeS) (CH-tBu) (OTf)₂) (8) wasprepared analogously to example 2, except using a corresponding amountof 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene rather than1,3-di-t-butylimidazol-2-ylidene.

Example 8 Preparation of Mo (N-2, 6-Me₂-C₆H₃) (IMesH₂)—(CHCMe₂Ph) (OTf)(OCH(CF₃)₂) (9)

Mo (N-2, 6-Me₂-C₆H₃) (CHCMe₂Ph) (OTf)₂(DME) (0.0400 g, 0.0420 mmol) wasdissolved in a minimal amount (˜2 mL) of C₂H₄Cl₂, the solution wascooled to −30° C. and then LiOCH(CF₃)₂ (0.0050 g, 0.0420 mmol) wasadded. The reaction mixture was stirred at room temperature for twohours and then filtered through Celite. After the solvent had beenremoved under reduced pressure, a yellow solid was obtained. The residuewas dissolved in a minimal amount of dichloromethane and crystallized at−30° C. for several days, in order to obtain yellow crystals (63%). ¹HNMR (CD₂Cl₂): δ=13.49 (s, 1H, CHCMe₂Ph, J_(CH)=114 Hz), 7.28-6.41 (m,14H, ArH), 3.97-3.82 (m, 4H, CH₂NC), 2.32-1.79 (s, 30H, Me); ¹³C NMR(CD₂Cl₂): δ 323.8 (CHCMe₃), 210.0 (CN_(carbene)), 155.2 (C_(ipso)),150.7, 139.5 (C_(ortho)) r, 136.9 (C_(aryl)), 135.8 (C_(aryl)), 135.2(C_(aryl)), 130.1 (C_(aryl)), 129.9 (C_(aryl)), 129.1 (C_(aryl)), 128.6(C_(aryl)), 127.8 (C_(aryl)), 126.6 (C_(aryl)), 125.8 (C_(aryl)), 121.6(CF₃), 118.4 (q, CF₃), 76.07-75.11 (q, OCH(CF₃)₂), 56.1 (CMe₂Ph), 51.9(CH_(2-imidazolylidene)), 37.2 (CMe₂Ph), 29.3 (CMe₂Ph), 21.5 (CH₃), 21.3(CH₃), 19.0 (CH₃), 18.9 (CH₃); ¹⁹F NMR (CD₂Cl₂): δ=−73.07-73.14 (q,CF₃), −77.33-73.40 (q, CF₃), −78.07 (s, CF₃SO₃, trans to the NHCligand). Elemental analysis: C₄₄H₅₀Cl₂F₉MoN₃O₄S; calculated: C, 50.05;H, 4.87; N, 3.98. found: C, 50.51; H, 4.85; N, 4.07.

Example 9 (Preparation of [Mo(N-2,6-Me₂-C₆H₃)—(CHCMe₂Ph) (OTf) (IMesH₂)⁺B(3,5-(CF₃)₂—C₆H₃)₄ ⁻] (10)

[Ag⁺ B(3,5-(CF₃)₂—C₆H₃)₄] (0.0874 g, 0.0879 mmol) was dissolved in 1 mLof C₂H₄Cl₂ and added at −30° C. to a solution of Mo(N-2,6-Me₂-C₆H₃)(CHCMe₂Ph) (OTf) (DME) (0.08370 g, 0.0879 mmol) in 2 mL of C₂H₄Cl₂. Thereaction mixture was stirred overnight, then filtered through Celite,and the solvent was removed under reduced pressure. The yellow residuewas taken up in a minimal amount of dichloromethane and stored at −30°C. for several days in order to isolate the product in the form ofyellow crystals in a ˜60% yield. ¹H NMR (CD₂Cl₂): δ=12.90 (s, 1H,CHCMe₂Ph, J_(CH)=127 Hz), 7.72-6.97 (m, 20H, ArH), 4.06 (s, 4H, CH₂NC),2.37-0.92 (s, 33H, Me); ¹³C NMR (CD₂Cl₂): δ=325.0 (CHCMe₃), 206.7(CN_(carbene)), 163.1-162.59 (q, ¹J_(B—C)=50 Hz), 154.0 (C_(ipso)),144.3, 143.2, 142.4, 141.3 (C_(ortho)), 137.1 (C_(aryl)), 135.4(C_(aryl)), 132.5 (C_(aryl)), 131.6 (C_(aryl)), 130.6 (C_(aryl)), 130.0(C_(aryl)), 129.6 (C_(aryl)), 129.2 (C_(aryl)), 129.0 (C_(aryl)), 128.8(C_(aryl)), 128.6 (C_(aryl)), 127.8 (C_(aryl)), 126.7 (C_(aryl)), 126.3(C_(aryl)), 123.8, 121.1, 118.1, 57.5 (CMe₂Ph), 52.8(CH_(2-imidazolylidene)), 28.8 (CMe₂Ph), 21.4 (CH₃), 21.3 (CH₃), 20.7(CH₃), 19.8 (CH₃), 18.7 (CH₃), 18.0 (CH₃). ¹⁹F NMR (CD₂Cl₂): δ=−62.89(s, 3F), −75.66 (s, CF₃SO₃, trans to the imido ligand).

Example 10 Preparation of Mo(N-2,6-Me₂-C₆H₃)(3-mesityl-1-(1-phenylethyl)imidazolin-2-ylidene) (CHCMe₂Ph)(OTf₂) (11)

3-Mesityl-1-(1-phenylethyl)-4,5-dihydrol-H-imidazol-3-iumtetrafluoroborate (0.0820 g, 0.2160 mmol) was suspended in 2 mL ofbenzene. KHMDS (0.0430 g, 0.2160 mmol) was added to the suspension whilestirring. After a reaction time of one hour, the clear benzene solutionwas filtered through Celite. Mo (N-2, 6-Me₂-C₆H₃)— (CHCMe₂Ph)(OTf₂)•(DME) (0.1580 g, 0.2160 mmol; J. Organomet. Chem. 1993, 459, 185)was dissolved in 8 mL of benzene and the solution was stirred for 15minutes. The previously filtered benzene solution of the free NHC wasthen added thereto, with observation of an immediate color change fromyellow to dark red. After stirring for three hours, the benzene wasremoved, and the yellow residue was washed with n-pentane and driedunder reduced pressure (0.0110 g, 85%). The residue was dissolved in aminimal amount of dichloromethane and stored at −30° C. for several daysin order to obtain yellow crystals (60%). ¹H NMR (CD₂Cl₂): δ=14.73 (s,1H, CHCMe₂Ph), 7.36-6.99 (m, 14H, ArH), 6.29 (s, 1H, Ar-Mes), 4.08-3.80(m, 4H, CH₂NC), 2.46-1.39 (s, 24H, Me); ¹⁹F NMR (CD₂Cl₂): δ=−77.06 (s,CF₃SO₃), −77.77 (s, CF₃SO₃, trans to the NHC ligand); elemental analysiscalculated for C₄₁H₄₇Cl₂F₆MoN₃O₆S₂; C, 48.14; H, 4.73; N, 4.10. found:C, 48.17; H, 4.68; N, 4.06.

Example 11 Preparation of Mo(N-2,6-Me₂-C₆H₃) (IMesH₂)—(CHCMe₃) (OTf)(OCH(CH₃)₂) (13)

Mo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CHCMe₃) (OTf)₂ (0.080 g, 0.0900 mmol) wasdissolved in a minimal amount (˜2 mL) of C₂H₄Cl₂, the solution wascooled to −30° C. and then LiOCH(CH₃)₂ (0.0050 g, 0.0900 mmol) wasadded. The reaction mixture was stirred at room temperature for twohours, then filtered through Celite, and the solvent was removed underreduced pressure. The yellow residue was taken up in a minimal amount ofdichloromethane and stored at −30° C. for several days in order toisolate the product in the form of yellow crystals in ˜63% yield.

The catalyst Mo (N-2, 6-Me₂-C₆H₃) (IMesH₂) (CHCMe₃) (OTf)-(OOCCF₃) (14)was prepared analogously to example 11, except using a correspondingamount of lithium trifluoroacetate instead of LiOCH(CH₃)₂.

Example 12 Preparation of Mo(N-2,6-Me₂-C₆H₃) (IMesH₂)—(CHCMe₃) (OTf)(OC₆H₅) (15)

Mo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CHCMe₃) (OTf)₂ (0.0300 g, 0.0315 mmol) wasdissolved in a minimal amount (˜2 mL) of C₂H₄Cl₂, the solution wascooled to −30° C. and then LiOC₆F₅ (0.0050 g, 0.0315 mmol) was added.The reaction mixture was stirred at room temperature for two hours andthen filtered through Celite. After the solvent had been removed underreduced pressure, a yellow solid was obtained. The residue was dissolvedin a minimal amount of dichloromethane and stored at −30° C. for severaldays in order to obtain yellow crystals.

Example 13 Preparation of Mo (N-2-tBu-C₆H₄) (IMesH₂)—(CHCMe₂Ph) (OTf)₂(12)

Mo (N-2-^(t)Bu-C₆H₄) (CHCMe₂Ph) (OTf) 2 (DME) (0.0320 g, 0.0430 mmol)was first dissolved in 2 mL of toluene.1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidin-2-ylidene (0.0130 g,0.0430 mmol) was dissolved 1 mL of toluene. A color change from yellowto light orange was observed here. After stirring for three hours, thetoluene was then removed and the residue was dried under reducedpressure. The product was isolated as a yellow solid.

Example 14 Preparation of Mo(NtBu)(Cl)₂(1,3-iPr₂-4,5-Cl₂-imidazol-2-ylidene) (pyridine)(CHCMe₃) (16)

Mo(NtBu) (Cl)₂(pyridine)₂(CHCMe₃) (0.036 g, 0.078 mmol) was dissolved in5 mL of dichloromethane. 1,3-Me₂-4,5-Cl₂-imidazol-2-ylidene-AgI (0.036g, 0.36 mmol, 1.0 equiv.) was added in solid form. The suspension wasstirred at room temperature for 1 hour. Subsequently, the suspension wasfiltered through Celite and the solvent was removed. The pale yellowsolids were taken up in 4 mL of dichloromethane and filtered once more.The solvent was removed and the solids were washed with n-pentane. Theproduct was obtained as a pale orange solid. Yield: 0.039 g (82%). ¹HNMR (400 MHz, CD₂Cl₂): δ=1.55 (s, br, 9H, tBu), 1.67 (s, br, 9H, tBu),1.71 (d, br, 12H, iPr-Me), 4.98 (m, br, 2H, iPr-CH), 7.56 (m, br, 2H,pyr), 8.02 (m, br, 1H, pyr), 9.21 (m, br, 1H, pyr), 9.86 (m, br, 1H,pyr), 14.38 (s, br, 1H, Mo═CH).

Example 15 Synthesis of Cat. 17

31.1 mg (0.076 mmol of1-(2,6-diisopropylphenyl)-3-(2-hydroxyphenyl)-4,5-dihydroimidazoliumtetrafluoroborate and 25.4 mg (0.152 mmol) of LiHMDS were suspended inbenzene. After the mixture had been stirred at room temperature for 1 h,the solids were filtered off and the filtrate was added dropwise to asolution of 60 mg (0.076 mmol) of Mo (N-2, 6-C₆H₃ ^(i)Pr₂) (CH₂CMe₂Ph)(OSO₂CF₃) 2(DME). The yellow solution darkened somewhat and becameslightly cloudy. The mixture was stirred at room temperature for 3 h andthen filtered through Celite. The solvent was removed under reducedpressure and the yellow solids obtained were dissolved in a littledichloromethane. Yellow crystals were obtained at −35° C. ¹H NMR(CD₂Cl₂, 400 MHz) δ=13.64 (s, 1H, CHCMe₂Ph, J_(CH)=119 Hz); 7.50-7.41(m, 2H, CH); 7.28-7.18 (m, 5H, CH); 7.17-7.01 (m, 7H, CH); 6.95 (dd,J=7.79, 1.32 Hz; 1H, CH); 4.60-4.47 (m, 1H, CH); 4.38-4.26 (m, 1H, CH);4.07-3.94 (m, 1H, CH); 3.93-3.80 (m, 1H, CH); 3.72-3.56 (m, 2H, CH);2.68 (hept, J=6.88 Hz; 1H, CH); 2.51 (hept, J=6.51 Hz; 1H, CH); 1.14 (d,J=6.81 Hz; 6H, CH₃); 1.03 (s, 3H, CH₃); 0.98 (d, J=6.84 Hz; 3H, CH₃);0.5 (d, J=6.81 Hz; 3H, CH₃); 0.84 (d, J=6.86 Hz; 6H, CH₃); 0.3 (d,J=6.74 Hz; 3H, CH₃); 0.6 (d, J=6.80 Hz; 3H, CH₃); 9F NMR (CD₂Cl₂)δ=−77.94 (SO₃CF₃); ¹³C NMR (CD₂Cl₂, 100 MHz) δ=316.9 (CH-Me₂Ph), 205.9(CN_(carbene)), 152.2 (C_(ar.)), 151.9 (C_(ar.)), 149.3 (C_(ar.)), 147.4(C_(ar.)), 146.5 (C_(ar.)), 145.7 (C_(ar.)), 137.2 (C_(ar.)), 130.3(C_(ar.)), 129.7 (C_(ar.)), 128.5 (C_(ar.)), 128.4 (C_(ar.)), 126.9(C_(ar.)), 126.7 (C_(ar.)), 126.6 (C_(ar.)), 126.4 (C_(ar.)), 125.3(C_(ar.)), 123.2 (C_(ar.)), 120.9 (C_(ar.)), 120.6 (C_(ar.)), 119.9 (q,CF₃, J=319 Hz), 117.5 (C_(ar.)), 55.6 (CH_(2-imidazolylidene)), 54.9(CH_(2-imidazolylidene)), 49.4 (CMe₂Ph), 34.8, 29.7, 28.7, 28.5, 26.6,26.1, 25.9, 24.3, 23.4, 22.7, 21.5.

Example 16 Synthesis of Cat. 18

30.03 mg (0.086 mmol) of1-(mesityl)-3-(2-hydroxyphenyl)-4,5-dihydroimidazolium tetrafluoroborateand 27.30 mg (0.163 mmol) of LiHMDS were suspended in benzene andstirred at room temperature for 2 h. The LiBF₄ formed was filtered offand the filtrate was slowly added dropwise to a solution of 60 mg (0.086mmol) of Mo(N-2, 6-C₆H₃Me₂) (CH₂CMe₂Ph) (OSO₂CF₃)₂-(DME) in benzene. Thereaction mixture was stirred at room temperature for 3 h and thenfiltered through Celite. The solvent was removed under reduced pressureand the residue was dissolved in a little dichloromethane. A couple ofdrops of n-pentane were added and the product was obtained at −35° C. asdark yellow crystals. ¹H NMR (CD₂Cl₂, 400 MHz) δ=(anti/syn 2:3) 14.46;12.81 (s, 1H, CHCMe₂Ph, J_(CH)=147 Hz (anti), 116 Hz (syn)); 7.31-7.13(m, 7H, CH); 7.11-7.02 (m, 2H, CH); 7.01-6.76 (m, 3H, CH); 6.70; 6.63(s, br, 1H, CH); 6.14; 6.02 (s, br, 1H, CH); 4.44-4.15 (m, 2H, CH₂);2.30 (s, CH₃); 2.22 (s, 3H, CH₃); 2.07 (s, CH₃); 2.05 (s, 3H, CH₃); 1.98(s, CH₃); 1.84 (s, CH₃); 1.70 (s, CH₃); 1.69 (s, CH₃); 1.57 (s, CH₃);1.44 (s, CH₃); 1.38 (s, CH₃); 1.30 (s, CH₃); ¹⁹F NMR (CD₂Cl₂) δ=−78.13(SO₃CF₃); −78.21 (SO₃CF₃); ¹³C NMR (CD₂Cl₂, 100 MHz) δ=330.2 (CH-Me₂Ph),309.3 (CH-Me₂Ph), 210.4 (CN_(carbene)), 208.1 (CN_(carbene)), 154.8(C_(ar.)), 154.6 (C_(ar.)), 153.6 (C_(ar.)), 151.8 (C_(ar.)), 147.8(C_(ar.)), 147.7 (C_(ar.)), 140.3 (C_(ar.)), 138.9 (C_(ar.)), 136.4(C_(ar.)), 136.1 (C_(ar.)), 136.0 (C_(ar.)), 135.6 (C_(ar.)), 135.5(C_(ar.)), 135.3 (C_(ar.)), 134.6 (C_(ar.)), 130.1 (C_(ar.)), 130.1(C_(ar.)), 130.0 (C_(ar.)), 129.7 (C_(ar.)), 129.4 (C_(ar.)), 129.3(C_(ar.)), 128.2 (C_(ar.)), 127.8 (C_(ar.)), 127.7 (C_(ar.)), 127.3(C_(ar.)), 126.7 (C_(ar.)), 126.7 (C_(ar.)), 126.6 (C_(ar.)), 126.5(C_(ar.)), 126.1 (C_(ar.)), 126.0 (C_(ar.)), 121.0 (C_(ar.)), 120.7(C_(ar.)), 120.4 (C_(ar.)), 120.1 (C_(ar.)), 120.0 (q, CF₃, J=319 Hz),120.0 (q, CF₃, J=320 Hz), 117.8 (C_(ar.)), 117.3 (C_(ar.)), 54.7(CH_(2-imidazolylidene)), 54.2 (CH_(2-imidazolylidene)), 51.7(CH_(2-imidazolylidene)), 51.3 (CH_(2-imidazolylidene)), 49.7 (CMe₂Ph),49.5 (CMe₂Ph), 32.4 (CH₃), 29.2 (CH₃), 29.2 (CH₃), 27.3 (CH₃), 21.1(CH₃), 21.0 (CH₃), 20.5 (CH₃), 19.0 (CH₃), 18.5 (CH₃), 18.0 (CH₃), 17.8(CH₃), 17.3 (CH₃).

Example 17 ROMP of 5,6-bis((pentyloxy)methyl)bicyclo-[2.2.1]hept-2-ene

To an initially charged solution of the monomer (0.05 g, 0.167 mmol) in2 mL of dichloromethane was added at room temperature, all at once, acatalyst solution of Mo(N-2,6-Me₂-C₆H₃) (IMesH₂)—(CHCMe₂Ph) (OTf)₂ (6)(0.0032 g, 0.0033 mmol) in 0.5 mL of dichloromethane. The mixture wasstirred for four hours and then the polymer was precipitated inn-pentane. The wash phase was concentrated and precipitated again. Thecolorless polymer was washed with n-pentane and dried (0.045 g, 90%). ¹HNMR (400 MHz, CDCl₃): δ=5.27-5.15 (m, 2H), 3.34 (brs, 10H), 2.70 (brs,1H), 2.31 (brs, 1H), 1.93 (brs, 2H), 1.54 (brs, 4H), 1.32 (brs, 8H),0.89 (brs, 6H). ¹³C NMR (101 MHz, CDCl₃): δ=134, 133.7, 71.25-70.25 (m),50.9-39.91 (m), 29.7, 29.6, 28.7, 22.7, 14.2; FT-IR (ATR, cm⁻¹): 2928(s), 2854 (s), 1460 (m), 1369 (m), 1104 (s), 967 (w), 734 (w);M_(n)=4000 g/mol, PDI=1.03, σ_(trans)=88%.

With Mo (N-2, 6-Me₂-C₆H₃) (IMes) (CHCMe₂Ph) (OTf)₂ (7) (0.0032 g, 0.0033mmol) in dichloromethane (0.5 mL) and the monomer (0.05 g, 0.167 mmol)in dichloromethane (2 mL), the polymer was isolated with a yield of 84%(0.042 g). ¹H NMR (400 MHz, CDCl₃): δ=5.27-5.17 (m, 2H), 3.34 (brs,10H), 2.70 (brs, 1H), 2.31 (brs, 1H), 1.93 (brs, 2H), 1.54 (brs, 4H),1.32 (brs, 8H), 0.89 (brs, 6H). ¹³C NMR (101 MHz, CDCl₃): δ=134, 133.7,71.12-70.63 (m), 47.60-39.92 (m), 29.7, 28.7, 22.7, 14.2; FT-IR (ATR,cm⁻¹): 2928 (s), 2854 (s), 1460 (m), 1369 (m), 1104 (s), 967 (w), 733(w); M_(n)=8200 g/mol, PDI=1.06, σ_(trans)=93%.

With Mo (N-2, 6-Me₂-C₆H₃) (IMesH₂) (CHCMe₂Ph) (OTf) (OCH (CF₃)₂) (9)(0.0026 g, 0.00271 mmol) in dichloromethane (0.5 mL) and the monomer(0.04 g, 0.1358 mmol) in dichloromethane (2 mL), the polymer wasprepared with a yield of 28% (0.012 g). ¹H NMR (400 MHz, CDCl₃):δ=5.27-5.17 (m, 2H), 3.34 (brs, 10H), 2.70 (brs, 1H), 2.31 (brs, 1H),1.93 (brs, 2H), 1.54 (brs, 4H), 1.32 (brs, 8H), 0.89 (brs, 6H). ¹³C NMR(101 MHz, CDCl₃): δ=134, 133.6, 71.11-70.11 (m), 47.60-39.78 (m), 29.6,29.5, 28.5, 22.6, 22.5, 14.2; FT-IR (ATR, cm⁻¹); 2928 (s), 2854 (s),1460 (m), 1369 (m), 1104 (s), 966 (w), 737 (w); M_(n)=11 400 g/mol,PDI=1.22, σ_(trans)=64%.

Example 18

The polymerization of the same monomer with Mo(N-2,6-Me₂-C₆H₃) (I-tBu)(CH-tBu) (OTf)₂ (2) (0.050 g of monomer, 2.6 mg of catalyst) affords thepolymer in 60% isolated yield (M_(n)=8500 g/mol), PDI=1.1,σ_(trans)=50%).

Example 19 ROMP of 7-oxabicyclo[2.2.1]hept-5-ene-2,3-diylbis(methylene)diacetate

A cooled solution (−35° C.) of Mo(N-2,6-Me₂-C₆H₃) (I-tBu)-(CH-tBu)(OTf)₂(2) (0.0045 g, 0.0050 mmol) in CH₂Cl₂ (0.5 mL) was added to a solutionof the monomer (0.0600 g, 0.2520 mmol) in CH₂Cl₂ (2 mL) at −30° C. After24 hours, the polymer was precipitated by adding pentane, washed withpentane and dried. Yield: 0.058 g (97%). FT-IR (ATR, cm⁻¹): 2902 (m),1732 (s), 1431 (w), 1366 (s), 1220 (s), 1104 (w), 1029 (s), 968 (s), 728(m). ¹H NMR (400 MHz, CDCl₃): δ 5.72-5.58 (m, 2H), 4.49 (brs, 1H), 4.18(m, 5H), 2.40 (brs, 2H), 2.03 (brs, 6H); ¹³C NMR (101 MHz, CDCl₃): δ170.8, 133.1, 81.4, 61.9, 45.8, 20.9. M_(n)=13 000 g/mol, PDI=1.7,σ_(trans)=85%.

Example 20

The polymerization of 0.050 g of the same monomer with 0.0032 g ofMo(N-2,6-Me₂-C₆H₃) (I-tBu)-(CH-tBu) (OTf)₂ (2) affords the polymer in35% yield (M_(n)=1800 g/mol, PDI=1.2, σ_(trans)=33%).

Example 21 ROMP of 2-(N-cyclohexylmethyl)norborn-5-ene

To a cooled solution (−30° C.) of 2-(N-cyclohexylmethyl)-norborn-5-ene(57.7 mg) in CH₂Cl₂ (2 mL) was added a solution of Mo(N-2,6-Me₂-C₆H₃)(IMesH₂) (CH-tBu) (OTf)₂ (1) (40 mg) in CH₂Cl₂ (0.5 mL). The reactionmixture was stirred at 80° C. for 24 h; then the polymer wasprecipitated by adding pentane, filtered off and dried (44.5 mg, 90%).FT-IR (ATR, cm⁻¹): 3270 (m), 2935 (s), 2860 (m), 2450 (m), 2075 (s),1681 (m), 1454 (s), 1225 (m), 1159 (s), 1030 (s), 807 (s), 636 (s); ¹HNMR (400 MHz, D₂O, hydrochloride salt): δ=6.40-5.86 (m), NH₂ ⁺ part ofthe D₂O signal at 4.7, 3.17 (b), 3.03-2.96 (m), 2.60-2.0 (b, m), 1.93(b), 1.74 (b), 1.40 (b), 1.28 (b); M_(n)=13 100 g/mol, PDI=1.10.

With Mo (N-2, 6-Me₂-C₆H₃) (IMesH₂)—(CHCMe₂Ph) (OTf)₂ (6) (0.0074 g,0.0078 mmol) and monomer (0.0400 g, 0.1951 mmol) in CH₂Cl₂ (3 mL), thepolymer was obtained in 70% yield (0.028 g). FT-IR (ATR, cm⁻¹): 3421(m), 2935 (s), 2858 (m), 2424 (m), 1630 (m), 1454 (s), 1222 (s), 1155(s), 1030 (s), 724 (s), 637 (s); ¹H NMR (400 MHz, CDCl₃): δ=8.69, 8.02,7.04, 6.92, 6.19, 5.79, 5.77, 5.36, 5.28, 4.52, 3.83, 3.10, 2.96, 2.80,2.36, 2.14, 2.00, 1.25, 0.86; ¹³C NMR (101 MHz, CDCl₃): δ=141.2, 138.8,134.9, 132.0, 130.3, 129.3, 58.1, 49.8, 48.6, 44.5, 42.3, 35.7, 34.3,24.8, 22.2, 17.8, 14.12.

With Mo (N-2, 6-Me₂-C₆H₃) (IMes) (CHCMe₂Ph) (OTf)₂ (7) (0.0075 g, 0.0078mmol) in dichloromethane (0.5 mL) and the monomer (0.04 g, 0.1951 mmol)in chloroform (2 mL), the polymer was obtained with ˜65% yield (0.026g). FT-IR (ATR, cm⁻¹): 3425 (m), 2920 (s), 2858 (m), 2424 (m), 1630 (m),1454 (s), 1222 (s), 1155 (s), 1030 (s), 724 (s), 637 (s); ¹H NMR (400MHz, CDCl₃): δ=8.64, 7.06, 6.22, 6.21, 5.69, 5.34, 3.09, 2.85, 2.34,2.17, 1.84, 1.82, 1.24, 0.88; ¹³C NMR (101 MHz, CDCl₃): δ=142.0, 138.8,134.0, 131.7, 129.8, 50.10, 42.68, 34.4, 24.1, 22.8, 14.

With Mo (N-2, 6-Me₂-C₆H₃) (IMesH₂) (CHCMe₂Ph) (OTf) (OCH (CF₃)₂) (9)(0.0082 g, 0.0078 mmol) in dichloromethane (0.5 mL) and the monomer(0.04 g, 0.1951 mmol) in dichloromethane (2 mL), the polymer wasisolated with a yield of 54% (0.022 g). ¹H NMR (400 MHz, CDCl₃): δ=6.97,6.17, 6.07, 5.79, 5.77, 5.35, 5.33, 4.54, 3.45, 3.18, 2.96, 2.82, 2.64,2.36, 2.31, 1.81, 1.60, 1.24; ¹³C NMR (101 MHz, CDCl₃): δ=140.7, 138.5,137.1, 136.6, 135.2, 132.3, 130.3, 58.2, 48.7, 45.0, 42.8, 42.6, 36.2,31.5, 29.0, 24.8, 21.0, 17.5, 14.4; FT-IR (ATR, cm⁻¹): 3421 (m), 2935(s), 2858 (m), 2424 (m), 1630 (m), 1454 (s), 1222 (s), 1155 (s), 1030(s), 724 (s), 637 (s).

Example 22 ROMP of 2-(N,N-dimethylaminomethyl)-norborn-5-ene)

To a cooled solution (−30° C.) of2-(N,N-dimethylaminomethyl)norborn-5-ene (79.7 mg) in CH₂Cl₂ (2 mL) wasadded a solution of Mo(N-2,6-Me₂-C₆H₃)—(IMesH₂) (CH-tBu) (OTf)₂ (1)(10.5 mg) in CH₂Cl₂ (0.5 mL). After stirring for 24 hours, the polymerwas precipitated by adding pentane and filtered off and dried. Yield: 27mg (34%). FT-IR (ATR, cm⁻¹): 2955 (s), 1629 (s), 1464 (s), 1259 (s),1151 (s), 1029 (s), 636 (s); ¹H NMR (400 MHz, DMSO-d⁶): δ=6.98, 5.42,3.14, 2.66, 2.32, 2.20, 2.17, 2.05, 0.85; M_(n)=10 500 g/mol, PDI=1.21.

Example 23 ROMP of norborn-5-ene-2,3-dimethanol

A solution of Mo (N-2,6-Me₂-C₆H₃) (IMesH₂) (CH-tBu) (OTf)₂ (1) (0.0173g, 0.0194 mmol) in CHCl₃ (1.5 mL) was added to a solution of the monomer(0.0300 g, 0.1940 mmol) in CHCl₃ (2 mL) at room temperature. Thereaction mixture was then stirred at 55° C. for 5 hours. Subsequently,the polymer is precipitated from pentane, washed with pentane and dried.Yield 80% (0.024 g). FT-IR (ATR, cm⁻¹): 3373 (s), 2930 (s), 2884 (s),1477 (m), 1261 (s), 1109 (s), 1023 (s), 921 (w), 632 (s); ¹H NMR (400MHz, DMSO-d⁶): δ 5.48-5.40 (m, 2H), 3.86 (brs, 2H), 3.44 (brs, 4H), 2.45(brs, 1H), 2.10 (brs, 1H), 1.83 (brs, 1H), 1.57 (brs, 1H), 1.33 (brs,1H). ¹³C NMR (101 MHz, CDCl₃): δ=134.8, 129.5, 69.4, 59.3, 47.8, 47.0,43.8, 43.4, 37.5 (b), 32.3; M_(n)=2800 g/mol, PDI=1.12.

Example 24 ROMP of bicyclo[2.2.1]hept-5-ene-2-carbaldehyde

A solution of Mo (N-2,6-Me₂-C₆H₃) (IMesH₂) (CH-tBu) (OTf)₂ (1) (0.006 g,0.0068 mmol) in CH₂Cl₂ (1.0 mL) was added to a solution of the monomer(0.0400 g, 0.3438 mmol) in CH₂Cl₂ (1.0 mL) at room temperature. Thereaction mixture was then stirred at room temperature for 20 hours.Subsequently, the reaction was quenched with MeOH:HCl (90:10 vol./vol.).The polymer thus precipitated was washed with pentane and dried. Yield:55% (0.022 g). FT-IR (ATR, cm⁻¹): 2942 (s), 2830 (m), 1720 (s), 1630(s), 1470 (s), 1255 (s), 1158 (s), 1026 (s), 719 (s), 636 (s); ¹H NMR(400 MHz, THF-d8): δ=9.53 (CHO), 6.13 (b), 5.95 (b), 4.62 (b), 2.75 (b);¹³C NMR (101 MHz, THF-ds): δ=204.6 (CHO), 141.2, 136.9, 131.9, 130.7,128.7, 43.2, 30.4, 21.2, 19.0, 17.9; M_(n)=5000 g/mol, PDI=2.1(M_(n,theor.)=6100 g/mol).

Example 25 General Method for the Cyclopolymerization of Diynes

The catalyst was dissolved in the solvent specified and this solutionwas added rapidly to one of the monomer in the same solvent. After 2hours, the polyreactions were terminated by addition of wet methanol.After a further 10 min, the polymer was precipitated by adding methanolor pentane and dried.

Example 26 Preparation ofpoly(4,4,5,5-tetrakis-(ethoxycarbonyl)-1,7-octadiyne)

The polymer was obtained according to example 25 usingMo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CH-tBu) (OTf)₂ (1) (3.6 mg, 0.004 mmol) andthe monomer (80 mg, 0.203 mmol) in 81% isolated yield (64 mg). IR(cm⁻¹): 2901 (m), 1730 (s), 1461 (m), 1444 (m), 1387 (m), 1363 (m), 1265(s), 1198 (m), 1122 (w), 1095 (m), 1052 (m), 1027 (s), 941 (m), 856 (m),781 (w), 703 (w); ¹H NMR (400 MHz, CDCl₃): δ=6.71 (s, 2H, CH), 4.41-4.25(bs, 8H, CH₂), 3.25-3.18 (bs, 4H, CH₂), 1.38-1.23 (bs, 12H, CH₃); ¹³CNMR (101 MHz, CDCl₃): δ=169.7, 130.8, 124.7, 61.7, 56.9, 32.5, 13.7;UV/Vis (CHCl₃): λ_(max)=484 nm. M_(n)=13 200 g/mol, PDI=1.9(M_(n,theor.)=19 700 g/mol).

It was possible to isolate the polymer through the use of Mo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CHCMe₂Ph) (OTf)₂ (6) (0.0036 g, 0.004 mmol)and the monomer (0.0800 g, 0.203 mmol) with 81% yield (64 mg). Thepolymerization was initiated at −30° C., and stirring was continued at80° C. for one hour. ¹H NMR (CDCl₃): δ=7.01 (br, m, 2H), 4.21 (br, m,8H), 3.18 (br, m, 4H), 1.28 (br, m, 12H); ¹³C NMR (CDCl₃): δ=169.9,131.0, 125.0, 61.9, 57.1, 32.7, 14.0; FT-IR (ATR, cm⁻¹): 2981 (m), 1729(s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s), 1027 (w), 945(s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl₃): λ_(max)=483 nm,M_(n)=15 000 g/mol, PDI=2.2, α insertion: ≧96%.

With the monomer (0.0400 g, 0.1014 mmol) and Mo(N-2,6-Me₂-C₆H₃) (IMes)(CHCMe₂Ph) (OTf)₂ (7) (0.0019 g, 0.0020 mmol), the polymer was preparedwith a yield of 75% (0.03 g). ¹H NMR (CDCl₃): δ=7.02 (br, m, 2H), 4.21(br, m, 8H), 3.18 (br, m, 4H), 1.27 (br, m, 12H); ¹³C NMR (CDCl₃):δ=169.9, 131.0, 125.0, 61.9, 57.1, 32.7, 14.0; FT-IR (ATR, cm⁻¹): 2981(m), 1729 (s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s), 1027(w), 945 (s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl₃):λ_(max)=481 nm, M_(n)=14 000 g/mol, PDI=1.8, α insertion: ≧96%.

With Mo (N-2, 6-Me₂-C₆H₃) (IMesH₂) (CHCMe₂Ph) (OTf) (OCH (CF₃)₂) (9)(0.0022 g, 0.0020 mmol) and the monomer (0.0400 g, 0.1014 mmol), thepolymer was likewise isolated with a yield of 75% (0.03 g). ¹H NMR(CDCl₃): δ=7.02 (br, m, 2H), 4.22 (br, m, 8H), 3.19 (br, m, 4H), 1.27(br, m, 12H); ¹³C NMR (CDCl₃): δ=169.9, 131.0, 125.0, 61.9, 57.1, 32.7,14.0; FT-IR (ATR, cm⁻¹): 2981 (m), 1729 (s), 1444 (w), 1368 (s), 1262(s), 1199 (w), 1092 (s), 1027 (w), 945 (s), 862 (w), 700 (w), 636 (w),579 (w). UV/Vis (CHCl₃): λ_(max)=482 nm, M_(n)=22 000 g/mol, PDI=2.1, αinsertion: ≧96%.

Example 27 Preparation of poly(2-(prop-2-yn-1-yl)-pent-4-ynoic acid)

The polymer was prepared from Mo (N-2,6-Me₂-C₆H₃)—(IMesH₂) (CHCMe₂Ph)(OTf)₂ (6) (0.0055 g, 0.0059 mmol) and the monomer (0.004 g, 0.294 mmol)with a yield of 65% (0.0260 g). The polymerization was initiated at −30°C. and stirring was continued at 80° C. for one hour. ¹H NMR (400 MHz,d₆-DMSO): δ=12.25, 7.07-6.84, 3.23, 2.34; ¹³C NMR (400 MHz, d₆-DMSO):δ=177.0, 135.4, 129.5, 71.1, 58.1; FT-IR (ATR, cm⁻¹): 2981 (m), 1729(s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s), 1027 (w), 945(s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl₃): λ_(max)=587,547 nm.

With Mo (N-2, 6-Me₂-C₆H₃) (IMes) (CHCMe₂Ph) (OTf)₂ (7) (0.0055 g, 0.0059mmol) and the monomer (0.0400 g, 0.294 mmol), the polymer was isolatedwith 55% yield (0.022 g). ¹H NMR (400 MHz, d₆-DMSO): δ=12.27, 6.68-6.76,3.23, 2.34; ¹³C NMR (400 MHz, d₆-DMSO): δ=177.0, 135.4, 129.5, 71.1,58.1; FT-IR (ATR, cm⁻¹: 2981 (m), 1729 (s), 1444 (w), 1368 (s), 1262(s), 1199 (w), 1092 (s), 1027 (w), 945 (s), 862 (w), 700 (w), 636 (w),579 (w). UV/Vis (CHCl₃): λ_(max)=587, 547 nm.

With the monomer (0.0400 g, 0.294 mmol) and Mo(N-2,6-Me₂-C₆H₃) (IMesH₂)(CHCMe₂Ph) (OTf) (OCH(CF₃)₂) (9) (0.0062 g, 0.0059 mmol), it waslikewise possible to obtain the polymer with a yield of 55% (0.022 g).¹H NMR (400 MHz, d₆-DMSO): δ=12.27, 6.68-6.76, 3.23, 2.34; ¹³C NMR (400MHz, d₆-DMSO): δ=177.0, 135.4, 129.5, 71.1, 58.1; FT-IR (ATR, cm⁻¹):2981 (m), 1729 (s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s),1027 (w), 945 (s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl₃):λ_(max)=587, 547 nm.

Example 28 Preparation of poly(2,2-di(prop-2-yn-1-yl)propane-1,3-diol)

The polymer was obtained using Mo(N-2,6-Me₂-C₆H₃)—(IMesH₂) (CH-tBu)(OTf)₂ (1) in 80% isolated yield (0.030 g). ¹H NMR (400 MHz, d₆-DMSO):δ=7.09-6.66 (m, 2H), 4.60 (brs, 2H), 3.17 (s, 2H), 2.08 (s, 2H). UV-vis:λ_(max)=593, 554 nm (DMSO).

With Mo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CHCMe₂Ph) (OTf)₂ (6) (0.010 g, 0.0105mmol) and the monomer (0.04 g, 0.2628 mmol), the polymer was preparedwith a yield of 70% (0.027 g). The polymerization was initiated at −30°C., and stirring was continued at room temperature for one hour. ¹H NMR(400 MHz, d₆-DMSO): δ=7.27-6.66, 4.42, 2.34, 2.29, 1.9; ¹³C NMR (101MHz, d₆-DMSO): 5=139.7, 135.4, 130.9, 129.4, 50.9, 20.5, 17.6, 17.2; IR(ATR mode, cm⁻¹): 3400 (w), 2977 (w), 1444 (w), 1367 (w), 1247 (m), 1159(m), 1065 (m), 946 (w), 856 (w), 629 (w). UV-vis: λ_(max)=593, 554 nm(DMSO); M_(n)=5000 g/mol, PDI=2.1.

In the case of use of Mo(N-2,6-Me₂-C₆H₃)—(IMes) (CHCMe₂Ph) (OTf)₂ (7)(0.010 g, 0.0105 mmol) and the monomer (0.0400 g, 0.2628 mmol), it waspossible to prepare the polymer with a yield of 65% (0.026 g). ¹H NMR(400 MHz, d₆-DMSO): δ=7.19-6.72, 2.86, 2.34, 2.26, 2.1, 1.82; ¹³C NMR(101 MHz, d₆-DMSO); δ=139.7, 135.4, 130.9, 129.4, 50.9, 20.5, 17.6,17.2; IR (ATR mode, cm⁻¹): 3420 (w), 2963 (w), 1465 (w), 1353 (w), 1233(m), 1122 (m), 1072 (m), 920 (w), 863 (w), 640 (w). UV-vis: λ_(max)=595,554 nm (DMSO); M_(n)=3900 g/mol, PDI=1.8.

In the case of use of Mo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CHCMe₂Ph) (OTf)(OCH(CF₃)₂) (9) (0.0011 g, 0.0052 mmol) and the monomer (0.0400 g, 0.212mmol), the polymer was isolated with 54% yield (0.022 g). IR (ATR mode,cm⁻¹): 3400 (w), 2977 (w), 1444 (w), 1367 (w), 1247 (m), 1159 (m), 1065(m), 946 (w), 856 (w), 629 (w). UV-vis: λ_(max)=593, 554 nm (DMSO);M_(n)=3000 g/mol, PDI=1.3.

Example 29 Poly(dipropargylmalonitrile)

A solution of Mo (N-2,6-Me₂-C₆H₃) (IMesH₂) (CH-tBu) (OTf)₂ (1) (0.016 g,0.0211 mmol) in CH₂Cl₂ (0.5 mL) was added to a solution of the monomer(0.0300 g, 0.211 mmol) in CH₂Cl₂ (2 mL) at −30° C. The mixture wasstirred at room temperature for 90 min, then quenched with MeOH—HCl(90:10, vol./vol.). The precipitated polymer was washed with pentane anddried. Yield: 60% (0.018 g). IR (cm⁻¹): 2960 (m), 2252 (w), 1588 (w),1484 (m), 1267 (s), 1232 (s), 1027 (s), 810 (w), 636 (s); ¹H NMR(DMSO-d₆): δ=7.5-6.5 (b), 53.8 (b); ¹³C NMR (DMSO-d₆): δ=160.2, 139.6,135.4, 130.8, 129.4, 50.9, 30.2, 20.6, 17.6; UV/Vis (DMSO): λ_(max)=530nm. M_(n)=1100 g/mol, PDI=1.15 (M_(n,theor.)=1420 g/mol).

Example 30 Poly(1,7-octadiyne-4,5-dicarboxylic acid

A solution of Mo (N-2,6-Me₂-C₆H₃) (IMesH₂) (CH-tBu) (OTf)₂ (1) (0.0137g, 0.0154 mmol) in CH₂Cl₂ (1.0 mL) was added to a solution of themonomer (0.0300 g, 0.1956 mmol) in THF (2 mL) at −30° C. The reactionmixture was stirred at room temperature for 1 hour, then the polymer wasprecipitated with pentane, washed with pentane and dried. Yield: 90%(0.034 g). IR (cm⁻¹): 3288 (m), 2918 (m), 1702 (s), 1431 (m), 1213 (s),1168 (s), 1026 (s), 946 (m), 634 (s); ¹³C NMR (CDCl₃): δ=174.8, 128-140(b), 40.4, 30.1; ¹³C NMR (LiOD/D₂O): δ=184.5, 132-128, 44.4, 30.5;UV/Vis (THF): λ_(max)=432 nm. M_(n)=2600 g/mol, PDI=1.3(M_(n,theor.)=2500 g/mol).

Example 31 Poly(4,4-bis(ethoxycarbonyl)-1,6-heptadiyne; poly(DEDPM)

The polymer was prepared using Mo (N-2,6-Me₂-C₆H₃)—(IMesH₂) (CH-tBu)(OTf)₂ (1) (4.5 mg, 0.0051 mmol) and the monomer (60 mg, 0.2540 mmol) in89% yield (53 mg). The polymerization was initiated at −30° C. and thenconducted at room temperature for a further hour. ¹H NMR (CDCl₃):δ=6.95-6.83 (s, 1H, CH), 6.45 (s, 1H, CH), 4.10-3.37 (bm, 6H, CH₂), 2.82(s, 1H, CH), 2.05-1.80 (m, 2H, CH₂), 1.17 (s, 3H); ¹³C NMR (CDCl₃):δ=170.9, 170.8, 169.0, 137.0, 123.2, 61.9, 58.2, 58.0, 57.3, 57.1, 54.3,54.1, 41.5, 29.7, 14.1; IR (ATR, cm⁻¹): 3367 (m), 2969 (s), 2929 (s),2864 (s), 1673 (s), 1519 (m), 1453 (m), 1366 (s), 1337 (w), 1258 (w),1190 (w), 1125 (s), 1077 (s), 947 (m), 770 (s), 690 (w); UV/Vis (CHCl₃):λ_(max)=548, 584 nm, α insertion: 81%, k_(p)/k_(i)=7.

With Mo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CHCMe₂Ph) (OTf)₂ (6) (0.004 g, 0.0042mmol) and monomer (0.05 g, 0.213 mmol), the polymer was obtained in 84%yield. ¹H NMR (400 MHz, CDCl₃): δ=6.68 (br m, 2H), 4.27 (br m, 4H), 3.43(br m, 4H), 1.30 (br m, 6H) ppm; ¹³C NMR (101 MHz, CDCl₃): δ=172.1,137.1, 128.4, 126.3, 123.3, 62.1, 57.4, 41.6, 14.2 ppm; IR (ATR mode,cm⁻¹): 2977 (w), 1720 (s), 1444 (w), 1367 (w), 1247 (m), 1159 (m), 1065(m), 946 (w), 856 (w), 629 (w). UV/Vis (CHCl₃): λ_(max)25=586, 546 nm.M_(n)=8500 g/mol, PDI=2.1, α insertion: ≧95%.

In the case of use of Mo(N-2,6-Me₂-C₆H₃)—(IMes) (CHCMe₂Ph) (OTf)₂ (7)(0.0040 g, 0.0042 mmol) and the monomer (0.0500 g, 0.212 mmol), it waspossible to isolate poly(DEDPM) with a yield of 86% (0.043 g). ¹H NMR(CDCl₃): δ=6.68 (br m, 2H), 4.27 (br m, 4H), 3.43 (br m, 4H), 1.31 (brm, 6H); ¹³C NMR (CDCl₃): δ=172.1, 138.7, 128.0, 125.8, 122.9, 62.1,57.4, 41.5, 14.2; FT-IR (ATR, cm⁻¹): 2979 (m), 1722 (s), 1446 (w), 1367(s), 1248 (s), 1158 (w), 1067 (s), 947 (s), 631 (m). UV/Vis (CHCl₃):λ_(max)=587, 546 nm. M_(n)=84 000 g/mol, PDI=2.8, α insertion: ≧99%.

In the case of use of Mo(N-2,6-Me₂-C₆H₃)—(IMesH₂) (CHCMe₂Ph) (OTf)(OCH(CF₃)₂) (9) (0.0040 g, 0.0042 mmol) with the monomer (0.0500 g,0.212 mmol), it was possible to isolate poly(DEDPM) with a yield of 54%(0.043 g). ¹H NMR (CDCl₃): δ=6.68 (br m, 2H), 4.27 (br m, 4H), 3.43 (brm, 4H), 1.31 (br m, 6H); ¹³C NMR (CDCl₃): δ=172.1, 137.1, 128.2, 126.4,123.3, 62.1, 57.4, 41.6, 14.2; FT-IR (ATR, cm⁻¹): 2977 (m), 1721 (s),1444 (w), 1367 (s), 1248 (s), 1158 (w), 1067 (s), 947 (s), 631 (m).UV/Vis (CHCl₃): λ_(max)=581, 546 nm, M_(n)=67 400 g/mol, PDI=2.7, αinsertion: ≧96%.

Example 32 Poly(4,4-bis[(3,5-diethoxybenzoyloxy)-methyl]-1,6-heptadiyne)

The polymer was prepared using Mo (N-2,6-Me₂-C₆H₃)—(IMesH₂) (CH-tBu)(OTf)₂ (1) (1.9 mg, 0.0022 mmol) and the monomer (60 mg, 0.1120 mmol) in94% yield (57 mg). The polymerization was initiated at −30° C. and thenconducted at room temperature for a further hour. ¹H NMR (CDCl₃):δ=7.04-6.92 (m, 4H), 6.71-6.60 (m, 2H), 6.45-6.31 (m, 2H), 4.44-4.31 (m,4H), 3.90-3.81 (m, 8H), 2.89-2.82 (m, 4H), 1.40-1.25 (m, 12H); ¹³C NMR(CDCl₃): δ=168.3, 159.3, 138.2, 131.2, 107.7, 107.6, 106.3, 63.6, 40.7,27.1, 14.7; IR (ATR, cm⁻¹): 3367 (m), 2969 (s), 2929 (s), 2864 (s), 1673(s), 1519 (m), 1453 (m), 1366 (s), 1337 (w), 1258 (w), 1190 (w), 1125(s), 1077 (s), 947 (m), 770 (s), 690 (w); UV/Vis (CHCl₃): λ_(max)=550,590 nm, α insertion: >91%; k_(p)/k_(i)=33.

It was possible to isolate the polymer through the use ofMo(N-2,6-Me₂-C₆H₃) (IMesH₂) (CHCMe₂Ph) (OTf)₂ (6) (0.0014 g, 0.0015mmol) and the monomer (0.04 g, 0.0745 mmol) in quantitative yield(0.0392 g). The polymerization was initiated at −30° C. and stirring wascontinued at 80° C. for one hour. ¹H NMR (CDCl₃): δ=6.90 (br, m, 4H),6.36 (br, m, 4H), 4.30 (brs, 4H), 3.85 (brs, 8H), 2.81 (brs, 4H), 1.29(brs, 12H); ¹³C NMR (CDCl₃): δ=168.5, 159.9, 138.3, 131.1, 123.4, 107.7,106.4, 69.6, 63.7, 43.4, 40.8, 14.8; FT-IR (ATR, cm⁻¹): 2978 (w), 1788(w), 1716 (s), 1592 (s), 1446 (m), 1385 (w), 1296 (m), 1216 (s), 1166(s), 1101 (m), 1051 (m), 990 (w), 817 (w), 757 (m), 675 (w), 619 (m);UV/Vis (CHCl₃): λ_(max)=591, 550 nm, α insertion: ≧93%.

With the monomer (0.0400 g, 0.754 mmol) and Mo(N-2,6-Me₂-C₆H₃) (IMes)(CHCMe₂Ph) (OTf)₂ (7) (0.0014 g, 0.0015 mmol), the polymer was preparedwith a yield of 60% (0.0255 g). ¹H NMR (CDCl₃): δ=6.90 (br, m, 4H), 6.36(br, m, 4H), 4.30 (br, s, 4H), 3.84 (br, S, 8H), 2.81 (br, s, 4H), 1.28(br, s, 12H); ¹³C NMR (CDCl₃): δ=166.5, 159.9, 138.5, 131.2, 123.4,107.7, 106.4, 69.6, 63.8, 43.4, 40.8, 14.5; FT-IR (ATR, cm⁻¹): 2978 (w),1787 (w), 1716 (s), 1591 (s), 1446 (m), 1385 (w), 1297 (m), 1216 (s),1166 (s), 1101 (m), 1051 (m), 990 (w), 817 (w), 757 (m), 674 (w), 618(m), UV/Vis (CHCl₃): λ_(max)=590, 550 nm, α insertion: ≧93%.

The polymer was prepared with Mo(N-2,6-Me₂-C₆H₃)—(IMesH₂) (CHCMe₂Ph)(OTf) (OCH(CF₃)₂) (9) (0.0015 g, 0.0015 mmol) and the monomer (0.0400 g,0.0745 mmol) with a yield of only 50% (0.020 g). ¹H NMR (CDCl₃): 5=6.90(br, m, 4H), 6.36 (br, m, 4H), 4.30 (br, s, 4H), 3.84 (br, s, 8H), 2.81(br, s, 4H), 1.28 (br, s, 12H); ¹³C NMR (CDCl₃): δ=166.4, 159.9, 138.3,131.2, 123.4, 107.6, 106.4, 69.5, 63.6, 43.4, 40.8, 14.8; FT-IR (ATR,cm⁻¹): 2978 (w), 1787 (w), 1716 (s), 1591 (s), 1446 (m), 1385 (w), 1297(m), 1216 (s), 1166 (s), 1101 (m), 1051 (m), 990 (w), 817 (w), 757 (m),674 (w), 618 (m), UV/Vis (CHCl₃): λ_(max)=591, 550 nm, α insertion:≧95%.

Example 33 General Procedure for the Reactions with the Catalysts 1-18Homo-Metathesis and Ring-Closing Metathesis (RCM):

The reactions are conducted in 1,2-dichloroethane (5 mL) and theappropriate substrates (see table 1). T=80° C.; catalyst:substrate(unless stated otherwise)=1:1000. The conversion was determined by GC-MSafter a reaction time of four hours. Internal standard: dodecane. Theresults of these studies are shown in table 1 below.

Ring-Opening Metathesis Polymerization (ROMP):

All reactions were conducted at 80° C. in 1,2-dichloroethane over aperiod of 4 hours. Monomer/catalyst=50:1. The results of these studiesare shown in table 2 below.

Cyclopolymerization of α,ω-Diynes:

All reactions were conducted at −30° C. to room temperature indichloromethane at a monomer/catalyst ratio of 50:1 and, unless statedotherwise, over a period of 1 hour. The results of these studies areshown in tables 3 to 7 below. The monomers used within the context ofthe ROMP and cyclopolymerizations are shown below:

TABLE 1 Turnover numbers of catalysts 9-14 in various olefin metathesisreactions. 9 10 11 12 13 14 Substrate Homo-metathesis (HM), (values inbrackets indicate the E fraction in %) Allyltrimethyl- 520 435 — — 460350 silane (60) (55) (60) (60) 1-Hexene 340 490 790  85 000^([c]) 660540 (100) (100) (100) (100) (100) (100) 140 000^([d])  (100) Styrene 6080 200 45 000^([d])  30 — (100) (100) (100) (100) 1-Octene 680 560 210000^([d]) 400 480 (85) (85) 150 000 (100) (100) (86) Ring-closingmetathesis (RCM) Diethyl diallyl 175  90   3200^([b])  150 350 malonateDiallyldi- 620 490 390 660 520 phenylsilane 1,7-Octadiene 140 920  4100^([b])  80 000^([c]) 830 650 100 000^([d]) N,N-Diallyl-t- 390  50270  0 butylcarbamide N,N-Diallyl-p- 180 160 420 250 350 tosylamideN,N-Diallyltri-  62 — —  15  0 fluoroacetamide Diallylmalo- 190  70 360100 150 nitrile Diallyl ether 220 245 690  0  0 ^([a])ClCH₂CH₂Cl, 80°C., 4 h, cat:substrate = 1:1000, ^([b])ClCH₂CH₂Cl, 80° C., 4 h,cat:substrate = 1:5000, ^([c])ClCH₂CH₂Cl, RT, overnight, cat:substrate =1:100 000, ^([d])ClCH₂CH₂Cl, RT, 1 h, cat:substrate = 1:500 000.

TABLE 2 Summary of the polymerization results with catalysts 9-11.Monomer:catalyst = 50:1. All reactions were conducted in CH₂Cl₂ at roomtemperature. Yield Selectivity M_(n) Monomer Catalyst (%) (cis/trans)(g/mol) PDI I 9 84 ≧95% 4000 1.03 I 10 86 ≧99% 8200 1.06 I 11 28 ≧64% 11400   1.22

TABLE 3 Reactivity of catalysts 8, 9 and 11 in the cyclopolymerizationof α,ω-diynes. Monomer:catalyst = 50:1 Mono- Solv./T Yield α M_(n) merCat. (° C.)/t (%) Selectivity (g/mol) PDI II 9 CH₂Cl₂, 84 ≧95% 8500 2.1−30° C.-RT, 1 h II 10 CH₂Cl₂, 86 ≧99% 84 000   2.3 −30° C.-RT, 1 h II 11CH₂Cl₂, 54 ≧96% 67 000   2.7 −30° C.-RT, 1 h III 9 CH₂Cl₂, 70 — 5000 2.1−30° C.-RT, 1 h III 10 CH₂Cl₂, 56 — 3900 1.8 −30° C.-RT, 1 h III 11CH₂Cl₂, 54 — 3000 1.3 −30° C.-RT, 1 h IV 9 CHCl₃, 81 96 15 000   2.2−30° C.-80° C., 1 h IV 10 CHCl₃, 75 96 14 000   1.8 −30° C.-80° C., 1 hIV 11 CHCl₃, 75 96 2200 2.1 −30° C.-80° C., 1 h V 9 CHCl₃, 65 — 3300 1.9−30° C.-80° C., 1 h V 10 CHCl₃, 55 — 2900 1.4 −30° C.-80° C., 1 h V 11CHCl₃, 55 — 6000 1.5 −30° C.-80° C., 1 h

TABLE 4 Cyclopolymerization of VI with initiator 6. Initiator M:IM_(n,exp) ^(a)) Yield α Selectivity trans st (I) ratio [g/mol] [%]^(b))PDI [%] [%] [%] 6 50:1 19 800 47 1.3 96 100 72 CH₂Cl₂, −30° C. to 20°C., 3 h. λ_(max) = 469 nm, poly-VI: M_(n,theo) = 27 900 g/mol. ^(a))GPCin CHCl₃, UV-vis detector, calibration against poly(styrene) standards;^(b))isolated, gravimetrically determined yields. st = syndiotactic.

TABLE 5 Cyclopolymerization of VII with initiator 6. Initiator M:IM_(n,exp) ^(a)) Yield α Selectivity trans it (I) ratio [g/mol] [%]^(b))PDI [%] [%] [%] 6 50:1 24 800 24 1.5 95 — 34 CH₂Cl₂, −30° C. to 20° C.,2 h. λ_(max) = 463 nm, poly-VII: M_(n,theo) = 27 900 g/mol. ^(a))GPC inCHCl₃, UV-vis detector, calibration against poly(styrene) standards;^(b))isolated, gravimetrically determined yields. it = isotactic.

TABLE 6 Cyclopolymerization of monomer III with initiator 6. Initiator(I) M:I ratio M_(n, exp) ^(a)) [g/mol] Yield [%]^(b)) PDI 6 50:1 9000 901.1 CH₂Cl₂, −30° C. to 20° C., 2 h. Poly-III: M_(n, theo) = 8300 g/mol.^(a))GPC in DMSO, UV-vis detector, calibration against poly(styrene)standards; ^(b))isolated, gravimetrically determined yields.

TABLE 7 Cyclopolymerization of monomer VIII with initiators 1 and 4. αInitiator M:I M_(n,exp) ^(a)) λ_(max) Yield Selectivity trans st (I)ratio [g/mol] [nm] [%]^(b)) PDI [%] [%] [%] 1 50:1 32 300 550; 832.1 >90 100 100 591 4 50:1 27 500 547; 77 1.8 >71 100 74 585 CH₂Cl₂,−30° C. to 20° C., 2 h. Poly-VIII: M_(n,theo) = 17 300 g/mol. ^(a))GPCin CHCl₃, UV-vis detector, calibration against poly(styrene) standards;^(b))isolated, gravimetrically determined yields.

Example 34 Immobilization of4-(hydroxymethyl)-1,3-dimesityl-4,5-dihydro-1H-imidazol-3-ium chloride(I1)

G60 silica gel (350 mg) were suspended in 10 mL of chloroform. A fewdrops of concentrated sulfuric acid were added thereto.4-(Hydroxymethyl)-1,3-dimesityl-4,5-dihydro-1H-imidazol-3-ium chloride(500 mg, 1.34 mmol) was dissolved in 10 mL of chloroform and added tothe reaction mixture. The reaction mixture was stirred at 60° C.overnight in order then to be cooled to room temperature and filtered.The solids obtained were washed repeatedly with CH₂Cl₂ and demineralizedwater. In order to remove residues of water, the solids were suspendedin dry THF and stirred for one hour. The solids were filtered off andwashed with diethyl ether. All volatile constituents were removed underreduced pressure. The solids were suspended in 20 mL of CH₂Cl₂, 1 mL oftrimethylsilyl chloride (8.14 mmol) was added to this solution, and themixture was stirred at room temperature overnight. All volatileconstituents were removed under reduced pressure, and the product wasobtained as a white solid.

Deprotonation of I1 to I2: I1 was suspended in 20 mL of THF. To this wasadded lithium hexamethyldisilazide (LiHMDS, 0.22 g, 1.34 mmol), and themixture was stirred at room temperature for two hours. The reactionmixture was filtered and the resulting solids were suspended in DMSO andstirred for 30 min. The solids were filtered off and washed repeatedlywith diethyl ether. All volatile constituents were removed under reducedpressure and the product was obtained as a pale yellow solid. ¹H MAS NMR(400.13 MHz): δ=6.59 (H_(arom)); 3.28 (CH₂, CH); 1.67, 0.87, 0.03 (CH₃).

Example 35 Immobilization of [Mo(N-2,6-Me₂C₆H₃)—(CHC(CH₃)₂Ph)(OTf)₂(DME)] on I2 (IMo-1)

Mo (N-2, 6-Me₂C₆H₃) (CHC(CH₃)₂Ph) (OTf)₂(DME) (100 mg, 0.14 mmol) wasdissolved in 3 mL of benzene. I2 was added to this solution and stirredat room temperature for three hours. The solvent was decanted off andthe solids were washed repeatedly with benzene, diethyl ether and CH₂Cl₂until the solvents were no longer colored. All volatile components wereremoved under reduced pressure and the product was obtained as an orangesolid. ¹H MAS NMR (400.13 MHz): δ=12.60 (CHCMe₂Ph); 6.88 (H_(arom));2.54 (CH₃, CH₂, CH); 0.13 (CH₃).

Example 36 Immobilization of [Mo(N-2,6-Cl₂C₆H₃)—(CHC(CH₃)₃) (OTf)₂(DME)]on 12 (IMo2)

Mo (N-2,6-Cl₂C₆H₃) (CHC(CH₃)₃) (OTf)₂(DME) (200 mg, 0.26 mmol) wasdissolved in 3 mL of benzene. I2 was added to this solution and stirredat room temperature for three hours. The solvent was decanted off andthe solids were washed repeatedly with benzene, diethyl ether and CH₂Cl₂until the solvents were no longer colored. All volatile components wereremoved under reduced pressure and the product was obtained as an orangesolid. ¹H MAS NMR (400.13 MHz): δ=13.77 (CHCMe₂Ph); 6.96 (H_(arom));2.69 (CH₃, CH₂, CH); 0.11 (CH₃).

Example 37 General Procedure for Metathesis Reactions with IMo1 and IMo2

The metathesis substrate was dissolved in CH₂Cl₂ (or ClH₂C—CH₂Cl) whichhad been filtered through Al₂O₃, and 50 μL of dodecane were added asinternal standard for GC-MS determination of conversion. The immobilizedcatalyst was suspended in CH₂Cl₂ (or ClH₂C—CH₂Cl) which had beenfiltered through Al₂O₃ and added rapidly to the solution preparedbeforehand. The reaction mixture was stirred at 40° C. (or 80° C.) for 4h. After cooling to room temperature, the reaction mixture was filteredthrough a glass fiber filter paper. For the GC-MS analysis, a sample wastaken directly from this solution. If the conversion was determined bymeans of NMR, no internal standard was added and the solvent was removedcompletely for the analysis.

Ratio Yield Turnover Substrate Initiator (cat:substrate) [%] number

IMo1 IMo2 1:563 1:590 38 90 210 532

IMo1 IMo2 1:1000 1:1000  3 12  30 120

IMo1 IMo2 1:440 1:305 41 30 184  90

IMo1 IMo2 1:1000 1:1000 10 10 100 100

IMo1 IMo2 1:448 1:478 24 48 106 217 Ratio Yield Turnover SubstrateInitiator (cat:substrate) [%] number trans:cis

IMo1 IMo2 1:481 1:836   68   4.3 327  37 1:0 1:0

IMo1 IMo2 1:571 1:548 100 100 571 548 1:1.3 1:1.1

IMo1 IMo2 1:123 1:76 100 100 123  76 1:0.6 1:0.7

IMo1 IMo2 1:251 1:59 100 100 251  59 1:9.4 1:21.8 Ratio Yield TurnoverSubstrate Initiator (cat:substrate) [%] number

IMo1 1:59 42 25

Structures of Tungsten-Oxo-Alkylidene-NHC Complexes Prepared

-   -   Mes=mesityl, OTf⁻=CF₃SO₃ ⁻,        BAr^(F)=tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        Me=methyl.

Example 38 Preparation of W(O)Cl₂(PPhMe₂) (IMes)-(CHCMe₂Ph) (W2)

W(O)Cl₂(PPhMe₂) (CHCMe₂Ph) (2.42 g, 3.56 mmol) was dissolved in 50 mL oftoluene. A solution of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene(1.08 g, 3.56 mmol, 1 equiv.) in 10 mL of toluene was prepared. Bothsolutions were cooled at −40° C. for 30 min. The cold NHC solution wasadded gradually to the stirred solution of W(O)Cl₂(PPhMe₂)₂(CHCMe₂Ph).The reaction mixture was stirred at room temperature for 2 h. Theslightly cloudy solution was filtered through Celite and the solvent wasremoved under reduced pressure. An orange oil was obtained. The oil wastaken up in 50 mL of dimethyl ether and filtered rapidly once again. Ayellow solid now begins to precipitate out. The solution was stored inthe refrigerator at −40° C. overnight. Yield: 2.63 g (87%) of a paleyellow solid. ¹H NMR (400 MHz, C₆D₆): δ=1.28 (d, 3H, PMe ₂, J_(P—H)=10.1Hz), 1.32 (s, 3H, CMe₂ Ph), 1.59 (s, 3H, CMe₂ Ph), 1.66 (d, 3H, PMe₂ ,J_(P—H)=10.3 Hz), 2.11 (s, 6H, Mes-Me), 2.24 (s, br, 6H, Mes-Me), 2.38(s, br, 6H, Mes-Me), 6.16 (s, br, 2H, N—CH═CH—N), 6.80 (s, br, 2H,Mes-Ar), 6.83 (s, br, 2H, Mes-Ar), 6.87 (m, 3H, CMe₂ Ph), 6.99-7.09 (m,5H, Ar), 7.25 (m, 2H, Ar), 7.46 (m, 2H, PMe₂Ph), 11.9 (d, 1H,J_(P—H)=3.6 Hz); ¹³C NMR (100 MHz, C₆D₆): δ=14.0 (d, PMe₂,J_(C—P)=34.8), 15.3 (d, PMe₂, J_(C—P)=31.2), 19.5 (o-Mes-Me), 19.7(o-Mes-Me), 21.2 (p-Mes-Me), 31.1 (CMe₂ Ph), 32.9 (CMe₂ Ph), 51.7(CMe₂Ph), 124.4 (br, N—C═C—N), 126.0 (p-CMe₂ Ph), 126.8 (o-CMe₂ Ph),128.2 (m-CMe₂ Ph), 128.5 (p-PPh), 129.3 (d, m-PPh, J_(C—P)=2.0 Hz),129.5 (d, o-PPh, J_(C—P)=2.7 Hz), 131.4 (d, ipso-PPh, J_(C—P)=8.6 Hz),135.9 (br), 137.6 (m-Mes), 138.7 (o-Mes), 152.3 (ipso-CMe₂ Ph), 193.1(d, N—C—N, J_(C—P)=71.1 Hz) 309.5 (W═C, J_(C—P)=125.3 Hz); ³¹P NMR (160MHz, C₆D₆): δ=8.28 (P—W), −33.2 (PMe₂Ph). CHN anal. calc. forC₃₉H₄₇Cl₂N₂OPW: C, 55.40; H, 5.60; N, 3.31. Found: C, 55.58; H, 5.74; N,3.32.

Example 39 Preparation of W(O) (OTf)Cl(PPhMe₂) (IMes)-(CHCMe₂Ph) (W3)

W(O)Cl₂(PPhMe₂) (IMes) (CHCMe₂Ph) (0.067 g, 0.08 mmol) was dissolved in2 mL of dichloromethane and cooled at −40° C. The cold solution wasadded to solid silver triflate (0.020 g, 1 equiv.) and stirredvigorously. A white precipitate formed. The suspension was stirred withexclusion of light for 30 minutes and filtered through Celite. After thesolvent had been removed, the yellow oil was taken up once again in 1 mLof dichloromethane and filtered once more. In order to remove residuesof silver chloride, the step has to be repeated a few times. Yield:0.061 g (81%) of a pale yellow solid. ¹H NMR (400 MHz, CD₂Cl₂): δ=0.97(s, 3H, CMe₂ Ph), 1.15 (d, 3H, PMe₂ , J_(P—H)=10.52 Hz), 1.36 (d, 3H,PMe₂ , J_(P—H)=10.53 Hz), 1.81 (s, 3H, CMe₂ Ph), 1.97 (s, 6H, Mes-Me),2.16 (s, 6H, Mes-Me), 2.39 (s, 6H, Mes-Me), 6.92 (s, br, 2H, Mes-Ar),6.93-7.10 (m, 2H, Ar), 7.11 (s, br, 2H, Mes-Ar), 7.11-7.16 (m, 2H, Ar),7.21-7.38 (m, 6H, Ar), 7.40 (s, 2H, N—CH═CH—N), 7.4-7.5 (m, 1H, Ar),10.08 (d, 1H, W═CH, J_(P—H)=2.2 Hz); ¹³C NMR (100 MHz, CD₂Cl₂): δ=11.60(d, PMe₂ , J_(C—P)=35.4), 13.9 (d, PMe₂ , J_(C—P)=31.2), 18.7(p-Mes-Me), 21.5 (o-Mes-Me), 28.7 (CMe₂ Ph), 32.7 (CMe₂ Ph), 52.0 (CMe₂Ph), 126.1, 126.3 (br, N—C═C—N), 128.0, 128.7, 129.5, 129.5, 129.6,129.6, 130.5 (d, PPh, J_(C—P)=26.3 Hz), 131.4 (d, PPh, J_(C—P)=9.3 Hz),131.7 (d, PPh, J_(C—P=)2.8 Hz), 134.5 (p-Mes), 135.4 (m-Mes), 136.5(o-Mes), 141.4, 147.9 (ipso-CMe₂ Ph), 191.1 (d, N—C—N, J_(C—P)=55.1 Hz),302.4 (d, W═C, J_(C—H)=116.9 Hz, J_(C—P)=9.5 Hz); 19F NMR (375 MHz,CD₂Cl₂) δ=−78.82 (OSO₂CF₃); ³¹P NMR (160 MHz, CD₂Cl₂): δ=17.34. CHNanal. calc. for C₄₀H₄₈ClF₃N₂O₄PSW: C, 50.04; H, 5.04; N, 2.92. Found: C,49.34; H, 4.80; N, 2.89.

Example 40 Preparation of W(O) (OCCH₃(CF₃)₂)Cl(IMes)-(CHCMe₂Ph)) (W4)

In the glovebox, W(O)Cl₂(PPhMe₂) (IMes) (CHCMe₂Ph) (0.568 g, 0.67 mmol)was initially charged in a 25 mL Schlenk flask. The compound wasdissolved in 10 mL of toluene and at −40° C. for 30 min. Subsequently,LiOCMe(CF₃)₂ (0.170 g, 0.67 mmol, 1 equiv.) was added in solid form. Thesuspension turned dark orange. After it had been stirred at roomtemperature for 3 h, the suspension was filtered and the solvent wasremoved. A dark orange oil was obtained. This was washed with 5 mL ofn-pentane and taken up in a minimal amount of diethyl ether. Thesolution was stored at −40° C. overnight. In the course of this, a paleyellow solid precipitated out. The solids were filtered off and themother liquor was concentrated further in order to precipitate a secondfraction of the product. The combined fractions can be recrystallizedonce more from diethyl ether. The product is obtained as a pale yellowsolid or as yellow crystals (0.470 g, 82%). ¹H NMR (400 MHz, C₆D₆):δ=1.49 (m, 3H, CMe(CF₃)₂), 1.54 (s, 3H, CMe₂ Ph), 1.60 (s, 3H, CMe₂ Ph),1.91 (s, 6H, Mes-Me), 2.05 (s, 6H, Mes-Me), 2.14 (s, 6H, Mes-Me), 5.97(s, 2H, N—CH═CH—N), 6.39 (s, br, 2H, Mes-Ar), 6.69 (s, br, 2H, Mes-Ar),7.00 (m, 5H, Ar), 9.76 (s, 1H, W═CH); ¹³C NMR (100 MHz, CD₂Cl₂): δ=17.3(OCMe(CF₃)₂), 19.1 (o-Mes-Me), 19.1 (o-Mes-Me), 21.3 (p-Mes-Me), 28.8(CMe₂ Ph), 33.4 (CMe₂ Ph), 50.3 (CMe₂ Ph), 78.4 (m, CMe(CF₃)₂, 3H),124.7 (N—C═C—N), 126.3 (p-CMe₂Ph), 126.6 (o-CMe₂ Ph), 128.5 (m-CMe₂ Ph),129.9, 135.6 (p-Mes), 135.9 (m-Mes), 137.2 (o-Mes), 140.5 (ipso-Mes),151.0 (CMe₂Ph), 192.1 (N—C—N), 282.1 (W═C, J_(C—H)=121.3 Hz); ¹⁹F NMR(375 MHz, C₆D₆): δ=−76.70-78.00 (dq). CHN anal. calc. forC₃₅H₃₉ClF₆N₂O₂W: C, 49.28; H, 4.61; N, 3.28. Found: C, 49.24; H, 4.73;N, 3.28.

Example 41 Preparation of W(O) (2,6-diphenylphenoxide)-Cl(IMes)(CHCMe₂Ph) (W5)

W(O)Cl₂(PPhMe₂) (IMes) (CHCMe₂Ph) (0.850 g, 1 mmol) was dissolved in 30mL of toluene. Lithium 2,6-diphenylphenoxide (0.266 g, 1.06 mmol, 1.05equiv.) was added in solid form at room temperature. The solution turnedcloudy. The reaction mixture was stirred at room temperature for 12 h.The toluene was reduced to half the volume and the colorless precipitatewas filtered off using Celite. The filtrate was concentrated furtheruntil precipitate formed again. The solution was stored in arefrigerator at −40° C. overnight. A yellow-orange solid was filteredoff (0.830 g, 90%). ¹H NMR (400 MHz, CD₂Cl₂): δ=1.33 (s, 3H, CMe₂ Ph),1.40 (s, 6H, Mes-Me), 1.55 (s, 3H, CMe₂ Ph), 1.80 (s, 6H, Mes-Me), 2.33(s, 6H, Mes-Me), 6.66 (m, 2H, Ar), 6.81 (s, 2H, N—CH═CH—N), 6.83 (s, br,2H, Mes-Ar), 6.86 (m, 1H, Ar), 6.89 (br, 2H, Mes-Ar), 6.97 (m, 4H, Ar),7.09 (m, 1H, Ar), 7.17 (m, 2H, Ar), 7.22-7.36 (m, 5H, Ar), 7.40 (m, 2H,Ar), 7.81 (m, 2H, Ar), 9.90 (s, 1H, W═CH); ¹³C NMR (100 MHz, CD₂Cl₂):δ=18.6 (o-Mes-Me), 19.2 (o-Mes-Me), 21.4 (p-Mes-Me), 29.6 (CMe₂ Ph),32.3 (CMe₂ Ph), 50.3 (CMe₂Ph), 120.5, 125.5, 126.4, 126.5, 127.1, 128.4,129.2, 129.3, 129.5, 130.5, 130.8, 131, 131.8, 133.2, 134.8, 135.4,135.4, 136.6, 139.8, 141.1, 142, 150.8 (ipso-CMe₂ Ph), 159.6(ipso-O—Ar), 191.6 (N—C—N), 288 (W═C, J_(CH)=123.1 Hz), 298.2(J_(C—H)=123.3 Hz). CHN anal. calc. for C₄₉H₄₉ClN₂O₂W: C, 64.16; H,5.38; N, 3.05. Found: C, 64.16; H, 5.41; N, 3.13.

Example 42 Preparation of [W(O) (CHCMe₂Ph) (IMes) (OTf)-(MeCN)₂B(3,5-(CF₃)₂—C₆H₃)₄] (W6)

The compound was prepared in situ, immediately prior to the catalysesconducted. W(O) (OTf)Cl(PPhMe₂) (IMes)-(CHCMe₂Ph) was dissolved in 5 mLof dichloromethane and cooled at −40° C. for 30 min. Subsequently,Ag(MeCN)₂B(Ar^(F))₄ (2.05 equiv.) was added in solid form. A colorlessprecipitate formed immediately. The suspension was stirred withexclusion of light at room temperature for 30 min. Thereafter, theprecipitate was filtered off using Celite. The intense yellow solutionwas used as catalyst stock solution. ¹H NMR (400 MHz, CD₂Cl₂): δ=1.49(s, 3H, CMe₂ Ph), 1.92 (s, 3H, CMe₂ Ph), 2.03 (s, 6H, MeCN), 2.12 (s,6H, Mes-Me), 2.18 (s, 6H, Mes-Me), 2.37 (s, 6H, Mes-Me), 6.96 (s, br,2H, Mes-Ar), 7.10 (s, br, 2H, Mes-Ar), 7.20-7.38 (m, 5H, Ar), 7.42 (s,2H, N—CH═CH—N), 7.63 (s, br, 4H, BAr^(F)), 7.80 (s, br, 8H, BAr^(F)),11.47 (s, 1H, W═CH); ¹³C NMR (100 MHz, CD₂Cl₂): δ=2.9 (MeCN), 18.5(o-Mes-Me), 19.0 (o-Mes-Me), 21.4 (p-Mes-Me), 29.2 (CMe₂ Ph), 31.0 (CMe₂Ph), 53.5 (CMe₂Ph), 118.2 (sept, J_(C—F)=3.8 Hz, p-CH (BAr^(F))), 125.3(q, J_(C—F)=272.4 Hz, 4×2CF₃ (BAr^(F))), 126.9, 127.2, 127.4, 129.2,129.7 (qq, J_(C—F)=31.6 Hz, J_(C—B)=2.7 Hz, 4×C—CF3 (BAr^(F))), 129.8,130.1, 130.9, 132.4, 134.6, 135.5 (s, br, 4×2C, o-CH (BAr^(F))), 136.9,141.7 (ipso-Mes), 148.8 (ipso-CMe₂Ph), 162.4 (q, J_(C—H)=49.8 Hz,4×BC(BAr^(F))), 187.0 (N—C—N), 324.3 (W═C, J_(C—H)=125.3 Hz); ¹⁹F NMR(375 MHz, CD₂Cl₂): δ=−62.77 (BAr^(f)), −77.82 (O—SO₂CF₃).

Example 43 Preparation of [W(O) (CHCMe₂Ph) (IMes)-OCCH₃(CF₃)₂)B(3,5-(CF₃)₂—C₆H₃)₄] (W7)

W(O) (OCCH₃(CF₃)₂)Cl(IMes) (CHCMe₂Ph) (0.032 g, 0.0375 mmol) wasdissolved in 5 mL of dichloromethane and cooled at −40° C. for 30 min.The solution was added to solid NaB(Ar^(F))₄ (0.0333 g, 1 equiv.). Thesuspension was stirred at room temperature for 30 min. A colorlessprecipitate formed. The solution was stored at −40° C. for 30 min andfiltered cold through a glass fiber filter. The filtrate wasconcentrated under reduced pressure to one third of the volume andfiltered once again. After the solvent had been removed, an orange oilwas obtained. The latter was stirred with n-pentane until an orangesolid formed. The pentane phase was decanted and the solids were driedunder reduced pressure. Yield: 0.055 g (87%). ¹H NMR (400 MHz, CD₂Cl₂):δ=1.29 (s, 3H, CMe₂Ph), 1.32 (sept, 3H, CCH₃ (CF₃)₂), 1.64 (s, 3H, CMe₂Ph), 1.94 (s, 6H, Mes-Me), 2.05 (s, 6H, Mes-Me), 2.37 (s, 6H, Mes-Me),7.02 (s, br, 2H, Mes-Ar), 7.16 (s, br, 2H, Mes-Ar), 7.18-7.31 (m, 5H,Ar), 7.57 (s, br, 4H, BAr^(F)), 7.68 (s, 2H, N—CH═CH—N), 7.74 (s, br,8H, BAr^(F)), 10.52 (s, 1H, W═CH); ¹³C NMR (100 MHz, CD₂Cl₂): δ=17.8(o-Mes-Me), 17.9 (o-Mes-Me), 19.3 (OCMe(CF₃)₂), 21.5 (p-Mes-Me), 29.4(CMe₂ Ph), 31.9 (CMe₂ Ph), 52.7 (CMe₂Ph), 86.3 (m, OCMe(CF₃)₂), 118.1(sept, J_(C—F)=3.8 Hz, p-CH (BAr^(F))), 123.8 (q, J_(C—F)=273.4 Hz,4×2CF₃ (BAr^(F))), 126.3 (N—C═C—N), 127.9 (o-Ar), 128.6 (p-Ar), 129.4(m-Ar), 129.5 (qq, J_(C—F)=31.6 Hz, J_(C—B)=2.7 Hz, 4×C—CF3 (BAr^(F))),131.1 (m-Mes), 131.2 (m-Mes), 133.0 (o-Mes), 134.3 (o-Mes), 135.3(p-Mes), 135.4 (s, br, 4×2C, o-CH (BAr^(F))), 143.6 (ipso-Mes), 147.6(ipso-CMe₂ Ph), 162.4 (q, J_(C—B)=49.8 Hz, 4×BC(BAr^(F))), 181.8(N—C—N), 297.3 (W═C, J_(C—H)=123.3 Hz); ¹⁹F NMR (375 MHz, CD₂Cl₂):δ=−62.86 (BAr^(F)), −78.61 (dq). CHN anal. calc. for C₆₇H₅₁BF₃₀N₂O₂W: C,47.88; H, 3.06; N, 1.67. Found: C, 47.96; H, 3.279; N, 1.84.

Example 44 Preparation of [W(O) (CHCMe₂Ph) (IMes)(2,6-diphenylphenoxide) B(3,5-(CF₃)₂—C₆H₃)₄)] (W8)

W(O) (2,6-diphenylphenoxide)Cl(IMes) (CHCMe₂Ph) (0.0171 g, 0.0186 mmol)was dissolved in 5 mL of dichloromethane and cooled at −40° C. for 30min. The solution was added to solid NaB(Ar^(F))₄ (0.0165 g, 1 equiv.).The suspension was stirred for 30 minutes. A colorless precipitateformed. The reaction mixture was cooled at −40° C. for 30 min andfiltered. The filtrate was concentrated down to one third and filteredonce again. After the solvent had been removed, a yellow foam wasobtained. This was stirred with n-pentane until a yellow precipitateformed. The pentane phase was decanted and the solids were dried underreduced pressure. Yield 0.029 g (89%). ¹H NMR (400 MHz, CD₂Cl₂): δ=0.72(s, 3H, CMe₂ Ph), 1.58 (s, 3H, CMe₂ Ph), 1.67 (s, 6H, Mes-Me), 1.71 (s,6H, Mes-Me), 2.34 (s, 6H, Mes-Me), 6.83 (s, br, 2H, Mes-Ar), 6.99 (s,br, 2H, Mes-Ar), 7.01-7.09 (m, 4H), 7.17-7.27 (m, 12H), 7.30-7.40 (m,4H), 7.45-7.52 (m, 1H), 7.56 (s, br, p-CH (BAr^(F))), 7.73 (s, 8H, o-CH(BAr^(F))), 11.82 (s, 1H, W═CH); ¹³C NMR (100 MHz, CD₂Cl₂, MeCN adduct):δ=2.5 (MeCN), 18.6 (o-Mes-Me), 18.9 (o-Mes-Me), 21.4 (p-Mes-Me), 30.1(CMe₂ Ph), 30.5 (CMe₂ Ph), 52.1 (CMe₂Ph), 118.1 (sept, J_(C—F)=3.8 Hz,p-CH (BAr^(F))), 123.5 (MeCN), 123.8 (q, J_(C—F)=273.4 Hz, 4×2CF₃(BAr^(F))), 126.7 (br, N—C═C—N), 126.8, 127.2, 128.8, 129.5 (qq,J_(C—F)=31.6 Hz, J_(C—B)=2.7 Hz, 4×C—CF3 (BAr^(F))), 129.9, 130.0,135.4, 135.4 (s, br, 4×2C, o-CH (BAr^(F))), 135.5, 135.6, 141.4(ipso-Mes), 147.3 (ipso-CMe₂ Ph), 157.5 (ipso-O—Ar), 162.4 (q,J_(C—B)=49.8 Hz, 4×BC(BAr^(F))), 188.6 (N—C—N), 309.9 (W═C,J_(C—H)=121.2 Hz); ¹⁹F NMR (375 MHz, CD₂Cl₂): δ=−62.87 (BAr^(F)). CHNanal. calc. for C₈₁H₆₁BF₂₄N₂O₂W: C, 55.75; H, 3.52; N, 1.61. Found: C,55.69; H, 3.913; N, 1.72.

Example 45 Preparation of [W(O) (CHCMe₂Ph) (IMes)-(OCCH₃(CF₃)₂) (MeCN)₂B(3,5-(CF₃)₂—(C₆H₃)₄] (W9)

The compound was prepared in situ, immediately before the catalysesconducted. W(O) (OCCH₃(CF₃)₂)Cl(IMes)-(CHCMe₂Ph) was dissolved in 5 mLof dichloromethane and cooled at −40° C. for 30 minutes. Subsequently,Ag(MeCN)₂B(Ar^(F))₄ (1.0 equiv.) was added in solid form. A colorlessprecipitate formed immediately. The suspension was stirred withexclusion of light at room temperature for 30 min. Thereafter, theprecipitate was filtered off using Celite. The intense yellow solutionwas utilized as catalyst stock solution.

Example 46 Preparation of [W(O) (CHCMe₂Ph) (IMes)(2,6-diphenylphenoxide) (MeCN)₂ B(3,5-(CF₃)₂—(C₆H₃)₄] (W10)

The compound was prepared in situ, immediately before the catalysesconducted. W(O) (2,6-diphenylphenoxide)-Cl(IMes)(CHCMe₂Ph) was dissolvedin 5 mL of dichloromethane and cooled at −40° C. for 30 minutes.Subsequently, Ag(MeCN)₂B(Ar^(F))₄ (1.0 equiv.) was added in solid form.A colorless precipitate formed immediately. The suspension was stirredwith exclusion of light at room temperature for 30 min. Thereafter, theprecipitate was filtered off using Celite. The intense yellow solutionwas utilized as catalyst stock solution.

Example 47 Preparation of [W(O)Cl₂(IMes) (CHCMe₂Ph) (W11)

W(O) (2,6-diphenylphenoxide)Cl(IMes) (CHCMe₂Ph) (0.023 g, 0.249 mmol)was dissolved in 2 mL of acetonitrile and cooled at −40° C. for 30minutes. Subsequently, a cold solution of AlCl₃ (0.0033 g, 0.249 mmol, 1equiv.) in 1 mL of acetonitrile was added. The solution turned intenseyellow and was stirred at room temperature for 3 h. Thereafter, thesolvent was removed and the oily residue was taken up in 1 mL ofdichloromethane. The solution was filtered and concentrated to 0.3 mL.After a few days, yellow crystals of the product formed. Yield: 0.013 g(74%).

Example 48 Preparation of W(O) (OTf) (OCCH₃(CF₃)₂) (IMes)-(CHCMe₂Ph)(W12)

W(O) (OCCH₃(CF₃)₂)Cl(IMes) (CHCMe₂Ph) (0.0495 g, 0.058 mmol) wasdissolved in 2 mL of dichloromethane and cooled at −40° C. for 30 min.Silver triflate (0.015 g, 0.058 mmol, 1 equiv.) was added to the coldsolution. A colorless precipitate was immediately observed. Thesuspension was stirred with exclusion of light for 1 h and filteredthrough Celite. The solvent was removed. A yellow oil remained, whichwas taken up in 1 mL of dichloromethane and filtered once again. Thisstep was repeated a few times in order to remove residues of silverchloride. The product is obtained as a yellow solid. Yield: 0.041 g(74%). ¹H NMR (400 MHz, CD₂Cl₂): δ=0.74 (s, 3H, CMe₂ Ph), 0.81 (s, 3H,CMe(CF₃)₂), 1.45 (s, 3H, CMe₂ Ph), 2.13 (s, 6H, Mes-Me), 2.18 (s, 6H,Mes-Me), 2.31 (s, 6H, Mes-Me), 6.96 (s, br, 2H, Mes-Ar), 7.03 (s, br,2H, Mes-Ar), 7.05-7.11 (m, 1H, Ar), 7.14-7.25 (m, 4H, Ar), 7.26 (s, 2H,N-CH═CH—N), 10.69 (s, 1H, W═CH); ¹³C NMR (100 MHz, CD₂Cl₂) δ=17.6(OCMe(CF₃)₂), 18.4 (o-Mes-Me), 18.5 (o-Mes-Me), 21.3 (p-Mes-Me), 29.0(CMe₂ Ph), 29.9 (CMe₂ Ph, 50.8 (CMe₂Ph), 82.3 (m, CMe(CF₃)₂), 125.8,126.1, 126.5, 128.6, 130.4, 130.4, 136.4 (p-Mes), 137.1 (m-Mes), 141.7(ipso-Mes), 150.9 (CMe₂Ph), 186.0 (N—C—N), 278.2 (W═C, J_(C—H)=127.1Hz); ¹⁹F NMR (375 MHz, C₆D₆): δ=−77.71 (s, br, OSO₂CF₃), −77.76 (m, br,OCCH₃(CF₃)₂).

Example 49 Preparation of W(O) (OTf)₂(IMes) (CHCMe₂Ph) (W13)

W(O)Cl₂(PPhMe₂) (IMes) (CHCMe₂Ph) (0.26 g, 0.83 mmol) was dissolved in 8mL of dichloromethane. The solution was cooled at −40° C. for 30 min.While stirring, Silver triflate (0.200 g, 0.766 mmol, 2.01 equiv.) wasadded in solid form. A colorless solid immediately precipitated out. Thesuspension was stirred with exclusion of light at room temperature for 1h. In the course of this, the color changed to yellow. The solution wasfiltered through Celite. The solvent was removed. A pale yellow foam wasobtained. The latter was dissolved in a small amount of dichloromethaneand filtered once again. This step was repeated a few times in order toremove silver chloride residues. The crude product can be recrystallizedfrom dichloromethane/diethyl ether. The product is obtained as a yellowcrystalline solid. Yield: 0.303 g (85%).

Example 50 Preparation of W(O) (2,6-diphenylphenoxide)₂(1,3-Me₂-4,5-Cl₂-imidazol-2-ylidene) (CHCMe₂Ph) (W14)

W(O) (2,6-diphenylphenoxide)₂(PMePh₂) (CHCMe₂Ph) (0.12 g, 0.117 mmol)was dissolved in 8 mL of toluene. 1,3-Me₂-4,5-Cl₂-imidazol-2-ylidene-AgI(0.048 g, 0.12 mmol, 1.01 equiv.) was added in solid form. Thesuspension was kept in an ultrasound bath at 70° C. for 1 hour.Subsequently, the suspension was filtered through Celite and the solventwas removed. The pale yellow solid was taken up in 4 mL ofdichloromethane and filtered once more. The solvent was removed and theoily solid was washed with n-pentane. The product was obtained as a paleorange solid. Yield: 0.1 g (86%). ¹H NMR (400 MHz, C₆D₆): δ=1.08 (s, 3H,CMe₂ Ph), 1.44 (s, 3H, CMe₂ Ph), 6.73-6.82 (m, 6H, Ar), 6.96-7.03 (m,8H, Ar), 7.05-7.12 (m, 6H, Ar), 7.17-7.28 (m, 12H, Ar), 7.47 (d, 2H,p-Ar, J=7.56 Hz), 7.47 (m, 4H, p-Ar), 10.25 (s, 1H, W═CH); ¹³C NMR (100MHz, C₆D₆): δ=29.4 (CMe₂ Ph), 31.5 (CMe₂ Ph), 36.3 (Me-NHC), 48.5(CMe₂Ph), 117.1 (NC═CN), 125.6, 125.8, 126.4, 126.8, 128.9, 129.8,130.4, 131.1, 132.1, 133.2, 133.4, 133.9, 140.6 (ipso-Ar), 142.0(ipso-Ar), 151.5 (ipso-CMe₂Ph), 157.8 (ipso-O—Ar), 163.4 (ipso-O—Ar),191.3 (N—C—N), 279.5 (W═C, J_(C—H)=124.0 Hz).

Example 51 Preparation ofW(NtBu)(Cl)₂(1,3-Me₂-4,5-Cl₂-imidazol-2-ylidene) (pyridine) (CHCMe₃)(W15)

W(NtBu) (Cl)₂ (pyridine)₂(CHCMe₃) (0.2 g, 0.36 mmol) was dissolved in 8mL of dichloroethane. 1,3-Me₂-4,5-Cl₂-imidazol-2-ylidene-AgI (0.145 g,0.36 mmol, 1.0 equiv.) was added in solid form. The suspension was keptin an ultrasound bath at 70° C. for 1 hour. Subsequently, the suspensionwas filtered through Celite and the solvent was removed. The pale yellowsolid was taken up in 4 mL of dichloromethane and filtered once more.The solvent was removed and the solids were washed with n-pentane. Theproduct was obtained as a pale orange solid. Two isomers form in equalproportions. Yield: 0.19 g (82%). ¹H NMR (400 MHz, CD₂Cl₂): δ=1.21 (s,9H, tBu), 1.28 (s, 9H, tBu), 1.38 (s, 9H, tBu), 1.41 (s, 9H, tBu), 3.76(s, 6H, Me ₂-NHC), 4.21 (s, 6H, Me ₂-NHC), 7.28 (m, 2H, pyr), 7.41 (m,2H, pyr), 7.68 (m, 1H, pyr), 7.86 (m, 1H, pyr), 8.60 (m, br, 2H, pyr),9.40 (m, 2H, pyr), 10.58 (s, 1H, W═CH), 12.0 (s, 1H, W═CH); ¹³C NMR (100MHz, CD₂Cl₂): δ=15.7, 31.0, 31.4, 31.4, 32.6, 34.3, 34.8, 39.2, 40.4,44.8, 45.4, 66.2 (CMe₃), 69.6 (CMe₃), 118.9, 119.0, 124.2, 124.8, 124.9,136.3, 139.1, 139.4, 150.5, 156.8, 157.1, 191.0 (N—C—N), 191.2 (N—C—N),279.9 (W═CH), 301.0 (W═CH).

Example 52 Preparation of W(NtBu)(Cl)(1,3-Me₂-4,5-Cl₂-imidazol-2-ylidene) (OHIPT)(CHCMe₃) (W16)

W(NtBu) (Cl)₂(1,3-Me₂-4,5-Cl₂-imidazol-2-ylidene)-(pyridine) (CHCMe₃)(0.15 g, 0.234 mmol) was dissolved in 8 mL of benzene. Lithium2,6-di(2,4,6-triisopropylphenyl)phenoxide (0.118 g, 0.234 mmol, 1.0equiv.) was added in solid form. The solution was stirred at roomtemperature overnight. A colorless precipitate formed. Subsequently, thesuspension was filtered through Celite and the solvent was removed. Thedark orange foam was taken up in 4 mL of toluene and filtered once more.The solvent was removed and the solids were recrystallized fromn-pentane. The product was obtained as an orange solid. Yield: 0.13 g(87%). ¹H NMR (400 MHz, C₆D₆): δ=0.72 (d, 3H, iPr), 1.00 (m, 6H, iPr),1.14 (d, 3H, iPr), 1.20 (s, 9H, tBu), 1.24 (s, 9H, tBu), 1.26 (m, 6H,iPr), 1.30 (m, 9H, iPr), 1.36 (m, 6H, iPr), 1.66 (m, 6H, iPr), 2.70-3.30(m, 10H, Me₂ -NHC, CH-iPr), 3.93 (m, 2H, CH-iPr), 6.9 (m, 1H, Ar), 7.02(m, 1H, Ar), 7.13 (m, 1H, Ar), 7.16 (m, 1H, Ar), 7.26 (m, 2H, Ar), 7.40(m, 1H, Ar), 10.37 (s, 1H, W═CH); ¹³C NMR (100 MHz, C₆D₆): δ=14.3, 22.3,22.7, 22.9, 24.2, 24.5, 24.7, 24.8, 25.2, 25.5, 27.1, 27.6, 30.4, 31.0,31.5, 34.2, 34.5, 34.6, 34.8, 43.8, 68.1 (CMe₃), 118.2, 119.7, 120.1,121.9, 122.7, 131.5, 132.0, 132.4, 138.1, 138.4, 147.2, 147.3, 147.4,148.1, 149.5, 149.9, 162.0, 192.0 (N—C—N), 281.9 (W═CH).

Example 53 Preparation of [W(NtBu) (1,3-Me₂-4,5-Cl₂-imidazol-2-ylidene)(OHIPT) (CHCMe₃) AlpftBu] (W17)

W(NtBu) (Cl) (1,3-Me₂-4,5-Cl₂-imidazol-2-ylidene) (OHIPT)-(CHCMe₃)(0.0331 g, 0.0323 mmol) was dissolved in 3 mL of dichloromethane.Lithium tetrakis(nonafluoro-t-butoxy)aluminate (LiAlpftBu, 0.0315 g,0.0323 mmol, 1.0 equiv.) was added in solid form. The solution wasstirred at room temperature for 1 h. A colorless precipitate formed. Atthe same time, the solution turned intense yellow. Subsequently, thesuspension was filtered through Celite and the solvent was removed. Theyellow foam was taken up in 4 mL of toluene and filtered once more. Thesolvent was removed and the yellow oil was stirred with n-pentane. Ayellow solid formed. The product was filtered off and dried underreduced pressure. Yield: 0.055 g (87%). ¹H NMR (400 MHz, CD₂Cl₂): δ=0.81(d, 6H, iPr), 0.95 (d, 6H, iPr), 0.99 (d, 6H, iPr), 1.01 (s, 9H, tBu),1.02 (d, 6H, iPr), 1.09 (s, 9H, tBu), 1.23 (d, 12H, iPr), 2.49 (sept,2H, CH-iPr), 2.58 (sept, 2H, CH-iPr), 2.89 (sept, 2H, CH-iPr), 3.29 (s,6H, Me₂ -NHC), 7.0 (m, 2H, Ar), 7.03 (m, 1H, Ar), 7.05 (s, 1H, Ar), 7.08(m, 2H, Ar), 7.15 (m, 1H, Ar), 10.74 (s, 1H, W═CH); ¹³C NMR (100 MHz,CD₂Cl₂): δ=24.2, 24.4, 24.5, 24.6, 24.8, 31.6, 32.7, 33.6, 34.7, 40.2,47.2, 74.4, 120.4, 122.0, 122.3, 122.8, 123.3, 124.9, 131.8, 132.6,133.2, 147.5, 147.8, 149.9, 158.6, 178.0, 289.0 (W═CH); ¹⁹F NMR (375MHz, CD₂Cl₂): δ=−75.72 (s, CF₃).

Example 54 General Method for In Situ Catalyst Syntheses

The tungsten oxo precursors W3-W5 (about 0.05 mmol) were dissolved in 2mL of 1,2-dichloroethane. An equimolar amount of Ag(MeCN)₂B(Ar^(F))₄(W4, W5) or 2 equiv. (W3) and/or excess AlCl₃ was added. The solutionwas stirred for 30 min and filtered. The filtrate was used as catalyststock solution.

Example 55 General Method for Ring-Closing, Homo- and Self-Metatheses

About 20 mg of the substrate were weighed into a 10 mL screwtop bottle.The appropriate amount of solvent was added (0.1 M solution).Thereafter, 0.5 equiv. of dodecane (internal standard) was added. Analiquot with 1 mg of substrate was taken for the t₀ sample. A 0.0005 Mcatalyst stock solution was prepared. The appropriate amount of stocksolution was added to the substrate solution. The solution was stirredat the given temperature for the given period of time. The reactionswere stopped by means of air atmosphere and a sample was taken for theGC-MS analysis. The exact monomer/catalyst compositions and the turnovernumbers (TONs) determined for these can be found in table 8.

Example 56 General Method for Cross-Metatheses (CM) withAllyltrimethylsilane

The same general method was followed as for the ring-closing metatheses(example 53). An additional 10 equivalents of allyltrimethylsilane weremerely added to the substrate. The exact monomer/catalyst compositionsand the turnover numbers (TONs) determined for these can likewise befound in table 8.

Example 57 Z-Selective Metathesis

In a protective gas box, 1-octene (about 22 mg) is weighed into a 4 mLscrewtop bottle and dissolved in 1 mL of benzene. While stirring, asolution of W17 (3.6 mg) in benzene (0.2 mL) is added. The mixture isstirred at room temperature for one hour. To monitor the course of thereaction and the selectivity, an aliquot is taken and diluted withundried CDCl₃ in order to stop the reaction. The reaction mixture wasanalyzed by ¹H NMR (100% conversion >99.9% Z-configured product).

TABLE 8 TONs with AlCl₃-activated 3-5 and with cationic complexes W6-W8.Reaction conditions, unless stated otherwise: T = 25° C. in1,2-dichloroethane for 4 h, ubstrate:catalyst 1:2000 Substrate W6 W7 W8W3^([a]) W4^([a]) W5^([a]) Ring-closing metathesis (RCM)Diallyldiphenylsilane 4800^([c]) 3400^([e]) 7600^([e]) 0^([c]) 0^([c])0^([c]) N,N-Diallyl-p- 1700^([c]) 1350 1700^([b]) 0^([c]) 0^([c])0^([c]) toluenesulfonamide Octa-1,7-diene  970^([c])  710 1500^([b])980^([c])  4300^([c])   4700^([c])   Diallylmalonitrile  130^([c])  6601400^([e]) 0^([c]) 0^([c]) 0^([c]) Diallyl ether   0   0 5700^([e])0^([c]) 0^([c]) 0^([c]) Diallyl thioether 4800^([c])   0 4900^([e])4800^([c])   1200    1400    4,4-Dicyanoocta-1,7-  470^([c])  4302600^([e]) 0^([c]) 0^([c]) 0^([c]) diene Diethyldiallyl 1600^([c])  6603200^([e]) 0^([c]) 0^([c]) 0^([c]) malonate Homometathesis (HM), inbrackets = E content (%) Allylbenzene 200 480 635 640 430 410 (55)^([c])(60) (85)^([e]) (55) (55) (80) 1-Hexene 2000 1640 5400 4900 5000 9800(60)^([c]) (65) (85)^([e]) (60)^([c]) (65)^([c]) (80)^([e]) 1-Octene3300 1320 6100 4830 5000 2000 (60)^([c]) (65) (85)^([e]) (55)^([c])(60)^([c]) (80)^([c]) Allylphenyl sulfide   0 0 300 0   0   280(>95)^([d]) (>95)^([d]) Trimethylallylsilane 4100 1710 1500 0   0   0  (55)^([c]) (55) (60) Cross-metathesis (CM)^([d]) withallyltrimethylsilane, in brackets = E content (%) Hex-5-en-1-yl acetate480 450 500 0   0   0   (55) (60) (80) 4-Octene 500 490 500 0   0   0  (50) (65) (80) N-Phenyl-(1-phenyl- 200   0   0 0   0   0  but-3-en-1-yl)amine (60) Self-metathesis (SM), in brackets = E content(%) Methyl oleate 1500   0^([c]) 10 000 0^([c]) 0^([c]) 0^([c]) (60)(70)^([f]) ^([a])activated with excess AlCl₃, CH₂Cl₂, room temperature,catalyst:substrate = 1:5000. ^([b])catalyst:substrate = 1:2000, 70° C.^([c])catalyst:substrate = 1:5000, 70° C. ^([d])catalyst:substrate =1:500, 25° C. ^([e])catalyst:substrate = 1:10 000, 25° C.^([f])catalyst: substrate = 1:20 000, 70° C.

1. An N-heterocyclic carbene complex of one of the general formulae I-IV

characterized in that A is NR² or PR², A² is CR^(2R), NR², PR², O or S,A³, N or P, C is a carbene carbon atom, the ring B is an unsubstitutedor a mono- or polysubstituted 5- to 7-membered ring which, as well asA¹, A² and/or A³, may contain further heteroatoms in the form ofnitrogen, phosphorus, oxygen or sulfur and wherein the substituents mayhave the definition described for R², the substituents R² and R^(2′) areindependently H, a linear, partly cyclic or branched C₁-C_(1B)-alkyl,especially a C₁-C₇-alkyl, a linear, partly cyclic or branchedC₂-C₁₈-alkenyl, especially a C₂-C₇-alkenyl, a C₃-C₂-cycloalkyl,especially a C₃-C₆-cycloalkyl, a linear, partly cyclic or branchedC₆-C₁₀₀-polyoxaalkyl, especially C₆-C₃₀-polyoxaalkyl, a C₅-C₁₄-aryl or-heteroaryl radical, a C₅-C₁₄-aryloxy, a linear, partly cyclic orbranched C₁-C₁₈-perfluoroalkyl, especially C₁-C₇-perfluoroalkyl, alinear, partly cyclic or branched C₁-C₁₈ perchloroalkyl, especially aC₁-C₇-perchloroalkyl, a linear, partly cyclic or branchedpart-fluorinated C₁-C₁₈-alkyl, especially a part-fluorinatedC₁-C₇-alkyl, a linear, partly cyclic or branched part-chlorinatedC₁-C₁₈-alkyl, especially a part-chlorinated C₁-C₇-alkyl, a per- orpart-fluorinated C₆-C₁₄-aryl, a per- or part-chlorinated C₅-C₁₄-arylradical, and, when A¹ and A² are each NR² or PR², R² may be the same ordifferent, or R² and R^(2′) together are a linear or branchedC₁-C₁-alkylene, especially a C₁-C₇-alkylene radical, M in the formulaeI, II, III and IV is Cr, Mo or W, X¹ and X² in formulae I to IV are thesame or different and are selected from the group comprising C₁-C₁₈carboxylates, C₁-C₁₈-alkoxides, fluorinated C₁-C₁₈ alkoxides, C₁-C₁₈mono- or polyhalogenated carboxylates, unsubstituted or mono- orpolysubstituted C₆-C₁₈ mono-, bi- or terphenoxides,trifluoromethanesulfonate, non-coordinating anions, especiallytetrakis(3,5-bis-(trifluoromethyl)phenyl)borate,tetrakis(penta-fluorophenyl)borate,tetrakis(nonafluoro-t-butoxy)-aluminate, tetrafluoroborate,hexafluorophosphate and hexafluoroantimonate, where the substituents onthe mono-, bi- or terphenoxides, in addition to halogen, may have thesame definition as R², Y is oxygen, sulfur, an N-adamantyl, anN-tert-butyl, a C₆-C₁₄—N-aryl radical, especially a C₆-C₁₀—N-arylradical, where the aryl radical may be mono- or polysubstituted byhalogen, a linear or branched C₁-C₁₈ alkyl, a linear or branched C₁-C₁₈alkyloxy or an unsubstituted or substituted phenyl radical wherein thesubstituents have the same definition as R², Z is a linear, partlycyclic or branched C₁-C₁₀-alkyleneoxy, especially a C₁-C₅-alkyleneoxy, alinear, partly cyclic or branched C₁-C₁₀-alkylenethio, especially aC₁-C₅-alkylenethio, a linear, partly cyclic or branchedC₁-C₁₀-alkylene-NR², especially a C₁-C₅-alkylene-NR², aC₆-C₁₀-aryleneoxy, a per- or part-fluorinated C₆-C₁₄-aryleneoxy, a per-or part-chlorinated C₆-C₁₄-aryleneoxy, a per- or part-brominatedC₆-C₁₄-aryleneoxy, a C₆-C₁₄-arylenethio, a per- or part-fluorinatedC₈-C₁₄-arylenethio, a per- or part-chlorinated C₆-C₁₄-arylenethio, aper- or part-brominated C₆-C₁₄-arylenethio or a C₆-C₁₄-arylene-NR², aper- or part-fluorinated C₆-C₁₄-arylene-NR², a per- or part-chlorinatedC₆-C₁₄-arylene-NR², a per- or part-brominated C₆-C₁₄-arylene-NR², aC₆-C₁₄-arylene-PR², a per- or part-fluorinated C₆-C₁₄-arylene-PR², aper- or part-chlorinated C₆-C₁₄-arylene-PR², a per- or part-brominatedC₆-C₁₄-arylene-PR², a carboxyl, a thiocarboxyl or a dithiocarboxylgroup, and R¹ and R^(1′) in the formulae I to IV are independently H,aliphatic, aromatic radical, linear or branched C₁-C₁₈ alkyl group,tert-butyl, CMe₂Ph group, unsubstituted or mono- or polysubstitutedC₆-C₁₄-aryl group, where the substituents have the definitions given forR², 2-(2-propoxy)phen-1-yl; 2-methoxyphen-1-yl; 2,4,5-trimethoxyphenyl;or ferrocenyl.
 2. A compound as claimed in claim 1, characterized inthat the ring B is a heterocycle selected from the group comprising1,3-disubstituted imidazol-2-ylidenes, 1,3-disubstitutedimidazolin-2-ylidenes, 1,3-disubstitutedtetrahydro-pyrimidin-2-ylidenes, 1,3-disubstituted diazepin-2-ylidenes,1,3-disubstituted dihydrodiazepin-2-ylidenes, 1,3-disubstitutedtetrahydrodiazepin-2-ylidenes, N-substituted thiazol-2-ylidenes,N-substituted thiazolin-2-ylidenes, N-substituted triazol-2-ylidenes,mono- or polysubstituted dihydrotriazol-2-ylidenes, mono- orpolysubstituted triazolin-2-ylidenes, N-substitutedthiadiazol-2-ylidenes, mono- or polysubstituted thiadiazolin-2-ylidenesand mono- or polysubstituted tetrahydrotriazol-2-ylidenes.
 3. A compoundas claimed in claim 1, characterized in that the ring B is bondedcovalently via a spacer group to a solid support.
 4. A compound asclaimed in claim 3, characterized in that the solid support is apolymeric support, especially based on PS-DVB, and the spacer group is aC₁-C₂₀-α,ω-dioxaalkylene or a C₁-C₂₀-alkyleneoxy group.
 5. A compound asclaimed in claim 3, characterized in that the solid support is aninorganic support, especially based on silicon dioxide, and the spacergroup is an alkyl-Si(O)₃ or an alkyl-SiR(O)₂ group in which R has thesame definition as R² in claim
 1. 6. A compound as claimed in claim 1,characterized in that R¹ in formulae I, II, III or IV is t-butyl, anunsubstituted or substituted phenyl or ferrocenyl or CMe₂Ph, R^(1′) inaddition to H may have all the definitions mentioned for R¹ and thesubstituents on the phenyl may have the same definition as R².
 7. Amethod of conducting an olefin metathesis reaction, the methodincluding: contacting a substrate for the olefin methathesis reactionwith a catalyst, wherein the catalyst is an N-heterocyclic carbinecomplex according to claim
 1. 8. The method as claimed in claim 7,wherein the olefin metathesis reaction is an asymmetric ordesymmetrizing ring-closing metathesis, a cross-metathesis, aring-opening cross-metathesis, a (cross-)ene-yne metathesis, aring-closing ene-yne metathesis, a cross-ene-diyne metathesis, a tandemring-opening-ring-closing metathesis, a ring-opening metathesispolymerization (ROMP), a 1-alkyne polymerization, an acyclic metathesispolymerization (ADMET) or a cyclopolymerization of α,ω-diynes.
 9. Themethod as claimed in claim 7, wherein the olefin metathesis reaction isan olefinolysis of fatty acid esters.
 10. The method as claimed in claim7, wherein the catalyst is a compound of formula II or IV and the methodfurther comprises: dissolving the compound of formula II or IV in anorganic solvent (I) or in an ionic liquid to form a solution, applyingthe solution in the form of a thin film to a support material,introducing the support material including the thin film into a reactionvessel (2), and introducing one or more substrates of the compound offormula II or IV into the reaction vessel, wherein the one or moresubstrate are dissolved in a solvent (II) that is immiscible with theorganic solvent (I) or the ionic liquid.
 11. The method as claimed inclaim 10, wherein the ionic liquids are 1,3-dimethyl-imidazolium salts,1,2,3-trimethylimidazolium salts, 1-butyl-3-methylimidazolium salts, or1-butyl-2,3-dimethylimidazolium salts, and the solvent immiscible withthe ionic liquid is toluene, pentane, hexane, heptane, octane, or acombination thereof.
 12. The method as claimed in claim 10, wherein theone or more substrates are charged continuously into the reaction vesseland the resulting reaction products are discharged continuouslytherefrom.
 13. The method as claimed in claim 10, the support materialis an inorganic support material or a polymer-organic support material.14. The method as claimed in claim 9, wherein the olefinolysis of fattyacid esters comprises the olefinolysis of vegetable oils and fats. 15.The method as claimed in claim 14, wherein the vegetable oils areselected from the group consisting of castor oil, palm oil, and coconutoil.
 16. The method as claimed in claim 15, wherein the vegetable oilsare combined with at least one of ethylene and butene.
 17. The method asclaimed in claim 13, wherein the inorganic support material comprisessilicon dioxide.
 18. The method as claimed in claim 13, wherein thepolymer-organic support material is a polymer-organic monolithic supportmaterial.